Photosensitive resin composition, method for producing hardened relief pattern, semiconductor device and display device

ABSTRACT

Provided is a photosensitive resin composition which comprises: (A-1) a resin containing a structure represented by general formula (1); and (B) a photo-acid generating agent. In general formula (1), X, R 1  to R 7 , m 1  to m 4 , n 1 , n 2 , Y and W are each as defined in the description.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a divisional of U.S. application Ser. No.14/363,557 filed Jun. 6, 2014, which is a U.S. National Stage ofInternational Patent Application No. PCT/JP2012/081691 filed Dec. 6,2012 which claims priority of Japanese Patent Application No.2012-057990 filed Mar. 14, 2012, Japanese Patent Application No.2011-290126 filed Dec. 28, 2011 and Japanese Patent Application No.2011-270661, filed Dec. 9, 2011. The disclosures of U.S. applicationSer. No. 14/363,557 and International Patent Application No.PCT/JP2012/081691 are incorporated by reference herein in theirentirety.

TECHNICAL FIELD

The present invention relates to a photosensitive resin composition foruse in the relief pattern formation, for example, of an insulatingmaterial in an electronic component and of a passivation film, a buffercoat film, an interlayer insulating film, etc., in a semiconductordevice, a method for producing a cured relief pattern by using thecomposition, a semiconductor device, and a display device.

BACKGROUND ART

Conventionally, a polyimide resin or benzoxazole resin excellent in allof heat resistance, electric properties, mechanical properties, etc., iswidely used for the surface protective film and interlayer insulatingfilm employed in a semiconductor device. These resins exhibit lowsolubility in various solvents and therefore, are generally used as acomposition after the resin in the form of a precursor prepared byring-opening the cyclic structure is dissolved in a solvent.Accordingly, a step of ring-closing the precursor is required when usingthe resin. This ring-closing step is usually carried out by heat curingunder heating at 300° C. or more.

However, in recent years, a semiconductor device inferior in the heatresistance compared with conventional products is being developed and inturn, lowering the heat curing temperature is required of the materialfor forming a surface protective film or an interlayer insulating film,as a result, the demand for heat curing at 300° C. or less, orfurthermore, heat curing at 250° C. or less is increasing.

To meet such a requirement, Patent Document 1 has proposed aphotosensitive resin composition excellent in the photosensitiveperformance, containing, as the base resin, a phenolic hydroxylgroup-containing alkali-soluble resin that is widely used as the baseresin in the resist field, and furthermore, containing a quinone diazidecompound and a curing agent, and it is disclosed that thisphotosensitive resin composition is heat-cured by heating at atemperature of 100 to 250° C. for 30 minutes to 10 hours.

Patent Document 2 also proposes a photosensitive resin compositioncontaining a novolak resin that uses a phenol compound having a benzenenucleus containing two or more hydroxyl groups and has a weight averagemolecular weight of 1,000 to 20,000, and a photosensitizing agent.

In addition, Patent Document 3 has proposed a reactive resin compositionusing a resin having, in the skeleton, a condensation product of abiphenyl compound with phenols, and using a photopolymerizationinitiator and/or a photoacid generator, which is a material excellent inelectrical properties and usable for forming a liquid crystalalignment-controlling bump and/or a spacer or forming a liquid crystalalignment-controlling bump and a spacer at the same time, and it isdisclosed that this reactive resin composition is heat-cured by heatingat a temperature of 150 to 400° C. for 10 to 120 minutes.

RELATED ART Patent Document

Patent Document 1: Japanese Unexamined Patent Publication (Kokai) No.2003-215789

Patent Document 2: Japanese Patent No. 3,839,840

Patent Document 3: Japanese Unexamined Patent Publication (Kokai) No.2008-292677

SUMMARY OF THE INVENTION Problems to be Solved by the Invention

In the case of applying a resin as a surface protective film or aninterlayer insulating film to a semiconductor device, elongation is animportant film property. However, the film obtained by curing thecomposition described in Patent Document 1 has a problem of lowelongation. Patent Document 2 is also silent on relief pattern formationwith a film having a thickness necessary for a semiconductor protectivefilm. In addition, the photosensitive resin composition described inPatent Document 2 has a problem that the elongation of cured film islow, the residual film ratio during heat curing is low and the curedpattern profile is bad.

Similarly to Patent Document 1, the film obtained by curing thecomposition of Patent Document 3 has been found to have a problem of lowelongation.

Accordingly, an object of the present invention is to provide aphotosensitive resin composition having sufficient alkali solubility,being curable at a temperature of 300° C. or less, ensuring excellentelongation of the cured film, enabling pattern formation with a thickfilm (about 10 μm), allowing a high residual film ratio during curing,and giving a good cured relief pattern profile, a cured relief patternforming method of forming a pattern by using the photosensitive resin,and a semiconductor device and a display device each having the curedrelief pattern.

Means to Solve the Problems

As a result of intensive studies and many experiments by taking intoaccount the problems in the conventional techniques, the presentinventors have found that the above-described object can be solved byusing a photosensitive resin composition comprising a copolymer havingspecific two kinds of repeating unit structures, or a resin mixture ofresins consisting of these specific repeating unit structures; and aphotoacid generator, and has accomplished the present invention, i.e.,the present invention is as follows.

[1]

A photosensitive resin composition comprising (A-1) a resin containing astructure represented by following formula (1) and (B) a photoacidgenerator:

{in formula (1), each X is independently a monovalent group selectedfrom the group consisting of a hydrogen atom, an alkoxycarbonyl grouphaving a carbon number of 2 to 20, an alkoxycarbonylmethyl group havinga carbon number of 2 to 20, an alkoxyalkyl group having a carbon numberof 2 to 20, a silyl group substituted with at least one alkyl grouphaving a carbon number of 1 to 10, a tetrahydropyranyl group, and atetrahydrofuranyl group; each m₁ is independently an integer of 1 to 3,each m₂ is independently an integer of 0 to 2, and 2≦(m₁+m₂)≦4; each ofm₃ and m₄ is independently an integer of 0 to 4; each of n₁ and n₂ isindependently an integer of 1 to 500, and n₁/(n₁+n₂) is from 0.05 to0.95 when m₁ is 2 or 3, and is from 0.35 to 0.95 when m₁ is 1; each R₁is independently a monovalent group selected from the group consistingof a hydrocarbon group having a carbon number of 1 to 10, an alkoxygroup having a carbon number of 1 to 10, a nitro group, a cyano group,and a group represented by following formula (5) or (6); when m₂ is 2,the plurality of R₁ may be the same as or different from each other;each of R₂ to R₅ is independently a hydrogen atom, a monovalentaliphatic group having a carbon number of 1 to 10, or a monovalentaliphatic group having a carbon number of 1 to 10, in which somehydrogen atoms or all hydrogen atoms are substituted with a fluorineatom; each of R₆ and R₇ is independently a halogen atom, a hydroxylgroup or a monovalent organic group; when m₃ is an integer of 2 to 4,the plurality of R₆ may be the same as or different from each other;when m₄ is an integer of 2 to 4, the plurality of R₇ may be the same asor different from each other; Y is a divalent organic group representedby following formula (3) or (4); W is a divalent group selected from thegroup consisting of a single bond, a chain aliphatic group having acarbon number of 1 to 10, a chain aliphatic group having a carbon numberof 1 to 10, in which some hydrogen atoms or all hydrogen atoms aresubstituted with a fluorine atom, an alicyclic group having a carbonnumber of 3 to 20, an alicyclic group having a carbon number of 3 to 20,in which some hydrogen atoms or all hydrogen atoms are substituted witha fluorine atom, an alkylene oxide group having from 1 to 20 repeatingunits, and groups represented by following formula (2):

and the polymer structure may be a random structure or a blockstructure};

—CR₈R₉—  (3)

(in formula (3), each of R₈ and R₉ is independently a hydrogen atom, amonovalent organic group having a carbon number of 1 to 11, or a groupcontaining a carboxyl group, a sulfonic acid group or a phenolichydroxyl group);

{in formula (4), each of R₁₁ to R₁₄ is independently a hydrogen atom, amonovalent aliphatic group having a carbon number of 1 to 10, or amonovalent aliphatic group having a carbon number of 1 to 10, in whichsome hydrogen atoms or all hydrogen atoms are substituted with afluorine atom; m₅ is an integer of 1 to 4; when m₅ is 1, R₁₀ is ahydroxyl group, a carboxyl group or a sulfonic acid group, and when m₅is an integer of 2 to 4, at least one R₁₀ is a hydroxyl group and theremaining R₁₀ are a halogen atom, a hydroxyl group, a monovalent organicgroup, a carboxyl group or a sulfonic acid group; and all R₁₀ may be thesame or different};

{in formula (5), R₁₅ is a monovalent group selected from the groupconsisting of a hydroxyl group, an aliphatic group having a carbonnumber of 1 to 12, an alicyclic group having a carbon number of 3 to 12,an aromatic group having a carbon number of 6 to 18, —NH₂, and groupsrepresented by —NH—R₁₉, —N(R₁₉)₂ and —O—R₁₉ (wherein R₁₉ is a monovalentgroup selected from an aliphatic group having a carbon number of 1 to12, an alicyclic group having a carbon number of 3 to 12, and anaromatic group having a carbon number of 6 to 18)};

{in formula (6), each of R₁₆ and R₁₇′ is independently a monovalentgroup selected from the group consisting of a hydrogen atom, analiphatic group having a carbon number of 1 to 12, an alicyclic grouphaving a carbon number of 3 to 12, and an aromatic group having a carbonnumber of 6 to 18, and R₁₆ and R₁₇′ may form a ring}.

[2]

The photosensitive resin composition according to [1], wherein informula (1), all X are a hydrogen atom.

[3]

A photosensitive resin composition comprising:

(A-2) a resin mixture including a resin containing a structurerepresented by following formula (7) and a resin containing a structurerepresented by following formula (8), and

(B) a photoacid generator,

wherein the weight ratio of the resin containing a structure representedby formula (7): the resin containing a structure represented by formula(8) is from 5:95 to 95:5:

{in formulae (7) and (8), each X is independently a monovalent groupselected from the group consisting of a hydrogen atom, an alkoxycarbonylgroup having a carbon number of 2 to 20, an alkoxycarbonylmethyl grouphaving a carbon number of 2 to 20, an alkoxyalkyl group having a carbonnumber of 2 to 20, a silyl group substituted with at least one alkylgroup having a carbon number of 1 to 10, a tetrahydropyranyl group, anda tetrahydrofuranyl group; each m₁ is independently an integer of 1 to3, provided that the plurality of m₁ are not 1 at the same time, each m₂is independently an integer of 0 to 2, and 2≦(m₁+m₂)≦4; each of m₃ andm₄ is independently an integer of 0 to 4; each of n₁ and n₂ isindependently an integer of 1 to 500; each R₁ is independently amonovalent group selected from the group consisting of a hydrocarbongroup having a carbon number of 1 to 10, an alkoxy group having a carbonnumber of 1 to 10, a nitro group, a cyano group, and a group representedby following formula (5) or (6); when m₂ is 2, the plurality of R₁ maybe the same as or different from each other; each of R₂ to R₅ isindependently a hydrogen atom, a monovalent aliphatic group having acarbon number of 1 to 10, or a monovalent aliphatic group having acarbon number of 1 to 10, in which some hydrogen atoms or all hydrogenatoms are substituted with a fluorine atom; each of R₆ and R₇ isindependently a halogen atom, a hydroxyl group or a monovalent organicgroup; when m₃ is an integer of 2 to 4, the plurality of R₆ may be thesame as or different from each other; when m₄ is an integer of 2 to 4,the plurality of R₇ may be the same as or different from each other; Yis a divalent organic group represented by following formula (3) or (4);W is a divalent group selected from the group consisting of a singlebond, a chain aliphatic group having a carbon number of 1 to 10, a chainaliphatic group having a carbon number of 1 to 10, in which somehydrogen atoms or all hydrogen atoms are substituted with a fluorineatom, an alicyclic group having a carbon number of 3 to 20, an alicyclicgroup having a carbon number of 3 to 20, in which some hydrogen atoms orall hydrogen atoms are substituted with a fluorine atom, an alkyleneoxide group having from 1 to 20 repeating units, and groups representedby following formula (2):

(in formula (3), each of R₈ and R₉ is independently a hydrogen atom, amonovalent organic group having a carbon number of 1 to 11, or a groupcontaining a carboxyl group, a sulfonic acid group or a phenolichydroxyl group);

{in formula (4), each of R₁₁ to R₁₄ is independently a hydrogen atom, amonovalent aliphatic group having a carbon number of 1 to 10, or amonovalent aliphatic group having a carbon number of 1 to 10, in whichsome hydrogen atoms or all hydrogen atoms are substituted with afluorine atom; m₅ is an integer of 1 to 4; when m₅ is 1, R₁₀ is ahydroxyl group; when n₅ is an integer of 2 to 4, at least one R₁₀ is ahydroxyl group and the remaining R₁₀ are a halogen atom, a hydroxylgroup, or a monovalent organic group; and all of R₁₀ may be the same ordifferent};

{in formula (5), R₁₅ is a monovalent group selected from the groupconsisting of a hydroxyl group, an aliphatic group having a carbonnumber of 1 to 12, an alicyclic group having a carbon number of 3 to 12,an aromatic group having a carbon number of 6 to 18, —NH₂, and groupsrepresented by —NH—R₁₉, —N(R₁₉)₂ and —O—R₁₉ (wherein R₁₉ is a monovalentgroup selected from an aliphatic group having a carbon number of 1 to12, an alicyclic group having a carbon number of 3 to 12, and anaromatic group having a carbon number of 6 to 18)};

{in formula (6), each of R₁₆ and R₁₇′ is independently a monovalentgroup selected from the group consisting of a hydrogen atom, analiphatic group having a carbon number of 1 to 12, an alicyclic grouphaving a carbon number of 3 to 12, and an aromatic group having a carbonnumber of 6 to 18, and R₁₆ and R₁₇′ may form a ring}.

[4]

The photosensitive resin composition according to [3], wherein informulae (7) and (8), all X are a hydrogen atom.

[5]

The photosensitive resin composition according to [3] or [4], whereinthe resin containing a structure represented by formula (7) contains astructure represented by following formula (9) and the resin containinga structure represented by formula (8) contains a structure representedby following formula (10):

{in formulae (9) and (10), each m₂ is independently an integer of 0 to2, provided that the plurality of m₂ are not 0 at the same time; each R₁is independently a monovalent group selected from the group consistingof a nitro group, a cyano group, and a group represented by formula (5)or (6); when m₂ is 2, the plurality of R₁ may be the same as ordifferent from each other; and R₂ to R₇, X, Y, W, m₃, m₄, n₁ and n₂ areas defined in formulae (7) and (8) above}.

[6]

The photosensitive resin composition according to [5], wherein informulae (9) and (10), all X are a hydrogen atom.

[7]

The photosensitive resin composition according to [1] or [2], wherein Yin formula (1) is a resin containing a structure represented byfollowing formula (11) or (12):

—CHR₈—  (11)

(wherein R₈ is a hydrogen atom or a monovalent organic group having acarbon number of 1 to 11);

(in formula (12), R₁₇ is a hydrocarbon group having a carbon number of 1to 10 or an alkoxy group having a carbon number of 1 to 10, m₆ is aninteger of 0 to 3, and when m₆ is 2 or 3, the plurality of R₁₇ may bethe same or different).

[8]

The photosensitive resin composition according to [3] or [4], wherein Yin formula (8) is a resin containing a structure represented byfollowing formula (11) or (12):

—CHR₈—  (11)

(in formula (11), R₈ is a hydrogen atom or a monovalent organic grouphaving a carbon number of 1 to 11);

(in formula (12), R₁₇ is a hydrocarbon group having a carbon number of 1to 10 or an alkoxy group having a carbon number of 1 to 10, m₆ is aninteger of 0 to 3, and when m₆ is 2 or 3, the plurality of R₁₇ may bethe same or different).

[9]

The photosensitive resin composition according to [5] or [6], wherein Yin formula (10) is a resin containing a structure represented by formula(11) or (12).

[10]

The photosensitive resin composition according to any one of [1], [2]and [7], wherein R₁ in formula (1) is at least one member selected fromthe group consisting of a hydrocarbon group having a carbon number of 1to 10, an alkoxy group having a carbon number of 1 to 10, and a grouprepresented by formula (5), W in formula (1) is a single bond, and R₁₅in formula (5) is a monovalent group selected from the group consistingof a hydroxyl group, —NH₂, and groups represented by —NH—R₁₉, —N(R₁₉)₂and —O—R₁₉ (wherein R₁₉ is a monovalent group selected from an aliphaticgroup having a carbon number of 1 to 12, an alicyclic group having acarbon number of 3 to 12, and an aromatic group having a carbon numberof 6 to 18).

[11]

The photosensitive resin composition according to any one of [3], [4]and [8], wherein R₁ in formulae (7) and (8) is at least one memberselected from the group consisting of a hydrocarbon group having acarbon number of 1 to 10, an alkoxy group having a carbon number of 1 to10, and a group represented by formula (5), W in formula (7) is a singlebond, and R₁₅ in formula (5) is a monovalent group selected from thegroup consisting of a hydroxyl group, —NH₂, and groups represented by—NH—R₁₉, —N(R₁₉)₂ and —O—R₁₉ (wherein R₁₉ is a monovalent group selectedfrom an aliphatic group having a carbon number of 1 to 12, an alicyclicgroup having a carbon number of 3 to 12, and an aromatic group having acarbon number of 6 to 18).

[12]

The photosensitive resin composition according to any one of [1], [2],[7] and [10], wherein resin (A-1) is a resin containing a structurerepresented by following formula (13):

{in formula (13), each m₂ is independently an integer of 0 to 2; each ofm₃ and m₄ is independently an integer of 0 to 4; each of n₁ and n₂ isindependently an integer of 1 to 500, and n₁/(n₁+n₂) is from 0.35 to0.8; each R₁ is independently a monovalent group having a carbon numberof 1 to 10 selected from a hydrocarbon group and an alkoxy group; whenm₂ is 2, the plurality of R₁ may be the same as or different from eachother; each of R₂ to R₅ is independently a hydrogen atom, a monovalentaliphatic group having a carbon number of 1 to 10, or a monovalentaliphatic group having a carbon number of 1 to 10, in which somehydrogen atoms or all hydrogen atoms are substituted with a fluorineatom; each of R₆ and R₇ is independently a halogen atom, a hydroxylgroup or a monovalent organic group; when m₃ is 2 to 4, the plurality ofR₆ may be the same as or different from each other; when m₄ is aninteger of 2 to 4, the plurality of R₇ may be the same as or differentfrom each other; Y is a methylene group or a structure represented byfollowing formula (14); and the polymer structure may be a randomstructure or a block structure}:

[13]

The photosensitive resin composition according to any one of [3], [4],[8] and [11], wherein the resin mixture (A-2) is a resin mixtureincluding a resin containing a structure represented by followingformula (15) and a resin containing a structure represented by followingformula (8a) and the weight ratio of the resin containing a structurerepresented by formula (15): the resin containing a structurerepresented by formula (8a) is from 35:65 to 80:20:

{in formulae (15) and (8a), m₁ is from 1 to 3; each m₂ is independentlyan integer of 0 to 2; each of m₃ and m₄ is independently an integer of 0to 4; each of n₁ and n₂ is independently an integer of 1 to 500; each R₁is independently a monovalent group having a carbon number of 1 to 10selected from a hydrocarbon group and an alkoxy group; when m₂ is 2, theplurality of R₁ may be the same as or different from each other; each R₂to R₅ is independently a hydrogen atom, a monovalent aliphatic grouphaving a carbon number of 1 to 10, or a monovalent aliphatic grouphaving a carbon number of 1 to 10, in which some hydrogen atoms or allhydrogen atoms are substituted with a fluorine atom; each of R₆ and R₇is independently a halogen atom, a hydroxyl group or a monovalentorganic group; when m₃ is from 2 to 4, the plurality of R₆ may be thesame as or different from each other; when m₄ is an integer of 2 to 4,the plurality of R₇ may be the same as or different from each other; andY is a methylene group or a structure represented by following formula(16)}:

[14]

A phenolic resin containing a structure represented by following formula(17):

{in formula (17), each of R₁ and R₁₇ is independently a monovalent grouphaving a carbon number of 1 to 10 selected from a hydrocarbon group andan alkoxy group; m₁ is an integer of 2 or 3, each of m₂ and m₆ isindependently an integer of 0 to 2, and 2≦m₁+m₂≦4; each of n₁ and n₂ isindependently an integer of 1 to 500 and satisfies 0.05≦n₁/(n₁+n₂)≦1;when m₂ is 2, the plurality of R₁ may be the same or different; and thepolymer structure may be a random structure or a block structure}.

[15]

A phenolic resin containing a structure represented by following formula(18):

{in formula (18), each R₁ is independently a monovalent group having acarbon number of 1 to 10 selected from a hydrocarbon group and an alkoxygroup; m₁ is an integer of 2 or 3, m₂ is an integer of 0 to 2, each ofn₁ and n₂ is independently an integer of 1 to 500, and these memberssatisfy 2≦m₁+m₂≦4 and 0.35≦n₁/(n₁+n₂)≦0.95; when m₂ is 2, the pluralityof R₁ may be the same or different; and the polymer structure may be arandom structure or a block structure}.

[16]

A photosensitive resin composition comprising the phenolic resinaccording to [14] or [15] and (B) a photoacid generator.

[17]

The photosensitive resin composition according to any one of [1] to [13]and [16], wherein photoacid generator (B) is a compound having anaphthoquinonediazide structure.

[18]

A photosensitive resin composition comprising (A-1) a resin containing astructure represented by following formula (19) and (B) a photoacidgenerator:

{in formula (19), each X is independently a monovalent group selectedfrom the group consisting of a hydrogen atom, an alkoxycarbonyl grouphaving a carbon number of 2 to 20, an alkoxycarbonylmethyl group havinga carbon number of 2 to 20, an alkoxyalkyl group having a carbon numberof 2 to 20, a silyl group substituted with at least one alkyl grouphaving a carbon number of 1 to 10, a tetrahydropyranyl group, and atetrahydrofuranyl group; each m₁ is independently an integer of 1 to 3,each m₂ is independently an integer of 1 to 2, and 2≦(m₁+m₂)≦4; each ofn₁ and n₂ is independently an integer of 1 to 500, and n₁/(n₁+n₂) isfrom 0.05 to 1; each R₁ is independently a monovalent group selectedfrom the group consisting of a nitro group, a cyano group, and a grouprepresented by following formula (5) or (6); when m₂ is 2, the pluralityof R₁ may be the same as or different from each other; m₇ is an integerof 0 to 2; R₁₈ is a hydroxyl group or a methyl group; when m₇ is 2, theplurality of R₁₈ may be the same as or different from each other; z isan integer of 0 or 1; Y is a methylene group or a structure representedby following formula (16); and the polymer structure may be a randomstructure or a block structure};

{in formula (5), R₁₅ is a monovalent group selected from the groupconsisting of a hydroxyl group, an aliphatic group having a carbonnumber of 1 to 12, an alicyclic group having a carbon number of 3 to 12,an aromatic group having a carbon number of 6 to 18, —NH₂, and groupsrepresented by —NH—R₁₉, —N(R₁₉)₂ and —O—R₁₉ (wherein R₁₉ is a monovalentgroup selected from an aliphatic group having a carbon number of 1 to12, an alicylcic group having a carbon number of 3 to 12, and anaromatic group having a carbon number of 6 to 18)};

{in formula (6), each of R₁₆ and R₁₇′ is independently a monovalentgroup selected from a hydrogen atom, an aliphatic group having a carbonnumber of 1 to 12, an alicyclic group having a carbon number of 3 to 12,and an aromatic group having a carbon number of 6 to 18, and R₁₆ andR₁₇′ may form a ring};

[19]

The photosensitive resin composition according to any one of [1] to [13]and [16] to [18], further comprising (C) a crosslinking agent.

[20]

The photosensitive resin composition according to any one of [1] to [13]and [16] to [19], further comprising (D) a thermal acid generator.

[21]

A method for producing a cured relief pattern, comprising the followingsteps:

(1) a step of forming, on a substrate, a photosensitive resin layercontaining the photosensitive resin composition according to any one of[1] to [13] and [16] to [20],

(2) a step of exposing the photosensitive resin layer to light,

(3) a step of removing the exposed area or unexposed area with adeveloper to obtain a relief pattern, and

(4) a step of heat-treating the relief pattern.

[22]

A cured relief pattern produced by the method according to [21].

[23]

A semiconductor device comprising a semiconductor element and a curedfilm provided on the top of the semiconductor element, wherein the curedfilm is the cured relief pattern according to [22].

[24]

A display device comprising a display element and a cured film providedon the top of the display element, wherein the cured film is the curedrelief pattern according to [22].

[25]

An alkali-soluble resin composition comprising an alkali-soluble resinand a solvent, wherein a cured film obtained by coating thealkali-soluble resin composition and curing the coated resin compositionat 200° C. satisfies all of following a) to c):

a) the stress at a film thickness of 7 μm is from 5 to 18 MPa,

b) the maximum value of tensile elongation of the film having a filmthickness of 10 μm is from 20 to 100%, and

c) the glass transition temperature at a film thickness of 10 μm is from180 to 300° C.

[26]

A cured product obtained by coating a substrate with a photosensitiveresin layer consisting of a positive-type photosensitive resincomposition containing a phenolic resin, a photoacid generator and asolvent and subjecting the layer to exposure, development and curing,wherein in a cross-sectional profile consisting of a space moiety of 5to 100 μm and a land moiety of 1 to 10 mm, the cross-sectional angledefined by an interior angle relative to the base material surface whena tangential line is drawn at a height of half the cured film thicknessis from 40 to 90°.

Effects of the Invention

According to the present invention, a photosensitive resin compositionhaving sufficient alkali solubility, being curable at a temperature of300° C. or less, ensuring excellent elongation of the cured film,enabling pattern formation with a thick film (about 10 μm), allowing ahigh residual film ratio during curing, and giving a good cured reliefpattern profile, and a semiconductor device and a display device eachhaving a cured relief pattern produced using the photosensitive resincomposition, can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 A ¹H NMR spectrum of Resin P1-1 described in Examples.

FIG. 2 A ¹H NMR spectrum of Resin P1-2 described in Examples.

FIG. 3 A ¹H NMR spectrum of Resin P2-1 described in Examples.

FIG. 4 A ¹H NMR spectrum of Resin P2-2 described in Examples.

FIG. 5 A ¹H NMR spectrum of Resin P2-3 described in Examples.

FIG. 6 A ¹H NMR spectrum of Resin P2-4 described in Examples.

FIG. 7 A ¹H NMR spectrum of Resin P2-6 described in Examples.

FIG. 8 A ¹H NMR spectrum of Resin P2-7 described in Examples.

FIG. 9 A ¹H NMR spectrum of Resin P4-3 described in Examples.

MODE FOR CARRYING OUT THE INVENTION

The best mode for carrying out the present invention (hereinafter,simply referred to as “embodiment”) is described in detail below. Thepresent invention is not limited to the following embodiment and can beimplemented by making various modifications within the scope of the gistthereof.

<Photosensitive Resin Composition>

In the embodiment, the photosensitive resin composition comprises (A-1)a resin or (A-2) a resin mixture, (B) a photoacid generator, (C) acrosslinking agent as desired, (D) a thermal acid generator as desired,and other components as desired. Respective components constituting thephotosensitive resin composition are described in detail below.Incidentally, throughout the description of the present invention, as tothe structure indicated by the same symbol in the formula, when aplurality of the structures are present in a molecule, they may be thesame or different.

[Resin (A-1)]

In the embodiment, resin (A-1) is a resin having a structure representedby following formula (1):

{in formula (1), each X is independently a monovalent group selectedfrom the group consisting of a hydrogen atom, an alkoxycarbonyl grouphaving a carbon number of 2 to 20, an alkoxycarbonylmethyl group havinga carbon number of 2 to 20, an alkoxyalkyl group having a carbon numberof 2 to 20, a silyl group substituted with at least one alkyl grouphaving a carbon number of 1 to 10, a tetrahydropyranyl group, and atetrahydrofuranyl group; each m₁ is independently an integer of 1 to 3,each m₂ is independently an integer of 0 to 2, and 2≦(m₁+m₂)≦4; each ofm₃ and m₄ is independently an integer of 0 to 4; each of n₁ and n₂ isindependently an integer of 1 to 500, and n₁/(n₁+n₂) is from 0.05 to0.95 when m₁ is 2 or 3, and is from 0.35 to 0.95 when m₁ is 1; each R₁is independently a monovalent group selected from the group consistingof a hydrocarbon group having a carbon number of 1 to 10, an alkoxygroup having a carbon number of 1 to 10, a nitro group, a cyano group, agroup represented by following formula (5), and a group represented byfollowing formula (6); when m₂ is 2, the plurality of R₁ may be the sameas or different from each other; each of R₂ to R₅ is independently ahydrogen atom, a monovalent aliphatic group having a carbon number of 1to 10, or a monovalent aliphatic group having a carbon number of 1 to10, in which some hydrogen atoms or all hydrogen atoms are substitutedwith a fluorine atom; each of R₆ and R₇ is independently a halogen atom,a hydroxyl group or a monovalent organic group; when m₃ is an integer of2 to 4, the plurality of R₆ may be the same as or different from eachother; when m₄ is an integer of 2 to 4, the plurality of R₇ may be thesame as or different from each other; Y is a divalent organic grouprepresented by following formula (3) or (4); W is a divalent groupselected from the group consisting of a single bond, a chain aliphaticgroup having a carbon number of 1 to 10, a chain aliphatic group havinga carbon number of 1 to 10, in which some hydrogen atoms or all hydrogenatoms are substituted with a fluorine atom, an alicyclic group having acarbon number of 3 to 20, an alicyclic group having a carbon number of 3to 20, in which some hydrogen atoms or all hydrogen atoms aresubstituted with a fluorine atom, an alkylene oxide group having from 1to 20 repeating units, and groups represented by following formula (2):

and the polymer structure may be a random structure or a blockstructure};

—CR₈R₉—  (3)

(in formula (3), each of R₈ and R₉ is independently a hydrogen atom, amonovalent organic group having a carbon number of 1 to 11, or a groupcontaining a carboxyl group, a sulfonic acid group or a phenolichydroxyl group);

{in formula (4), each of R₁₁ to R₁₄ is independently a hydrogen atom, amonovalent aliphatic group having a carbon number of 1 to 10, or amonovalent aliphatic group having a carbon number of 1 to 10, in whichsome hydrogen atoms or all hydrogen atoms are substituted with afluorine atom; m₅ is an integer of 1 to 4; when m₅ is 1, R₁₂ is ahydroxyl group, a carboxyl group or a sulfonic acid group, and when n₅is an integer of 2 to 4, at least one R₁₂ is a hydroxyl group and theremaining R₁₂ are a halogen atom, a hydroxyl group, a monovalent organicgroup, a carboxyl group or a sulfonic acid group; and all R₁₀ may be thesame or different);

{in formula (5), R₁₅ is a monovalent group selected from the groupconsisting of a hydroxyl group, an aliphatic group having a carbonnumber of 1 to 12, an alicyclic group having a carbon number of 3 to 12,an aromatic group having a carbon number of 6 to 18, —NH₂, and groupsrepresented by —NH—R₁₉, —N(R₁₉)₂ and —O—R₁₉ (wherein R₁₉ is a monovalentgroup selected from an aliphatic group having a carbon number of 1 to12, an alicyclic group having a carbon number of 3 to 12, and anaromatic group having a carbon number of 6 to 18));

{in formula (6), each of R₁₆ and R₁₇′ is independently a monovalentgroup selected from the group consisting of a hydrogen atom, analiphatic group having a carbon number of 1 to 12, an alicyclic grouphaving a carbon number of 3 to 12, and an aromatic group having a carbonnumber of 6 to 18, and R₁₆ and R₁₇′ may form a ring}.

In formula (1), each X is independently a monovalent group selected fromthe group consisting of a hydrogen atom, an alkoxycarbonyl group havinga carbon number of 2 to 20, an alkoxycarbonylmethyl group having acarbon number of 2 to 20, an alkoxyalkyl group having a carbon number of2 to 20, a silyl group substituted with at least one alkyl group havinga carbon number of 1 to 10, a tetrahydropyranyl group, and atetrahydrofuranyl group. Among others, in view of sensitivity, X ispreferably a hydrogen atom, a tert-butoxycarbonyl group, atert-butoxycarbonylmethyl group, a tetrahydropyranyl group, or atetrahydrofuranyl group, and in view of heat resistance, more preferablya hydrogen atom.

In formula (1), each m₁ is independently an integer of 1 to 3. In viewof alkali solubility and the profile of cured relief pattern, m₁ ispreferably 2 or 3, and in view of lithography, m₁ is more preferably 2.In order to facilitate interaction of phenolic resin (A-1) withphotoacid generator (B), when m₁ is 2, the bonding-position relationshipbetween hydroxyl groups in formula (1) is preferably the meta-position.

In formula (1), R₁ is not limited as long as each R₁ is independently amonovalent group having a carbon number of 1 to 10 selected from ahydrocarbon group and an alkoxy group, a nitro group, a cyano group, agroup represented by following formula (5), and/or a group representedby following formula (6).

In the case where R₁ is a monovalent group having a carbon number of 1to 10 selected from a hydrocarbon group and an alkoxy group, in view ofheat resistance, R₁ is preferably a hydrocarbon group or alkoxy grouphaving a carbon number of 1 to 5, more preferably a hydrocarbon grouphaving a carbon number of 1 to 3.

In the case where R₁ is an electron-withdrawing group, such as nitrogroup, cyano group, a group represented by formula (5), and a grouprepresented by formula (6), the acidity of the phenolic hydroxyl grouprises, and the photosensitive resin composition formed gives a coatingfilm excellent in alkali solubility. In the description of the presentinvention, the electron-withdrawing group indicates an atomic group ofwhich power to attract an electron from a target by a resonance effector an inductive effect is higher than that of a hydrogen atom. Inaddition, even when the phenolic resin is increased in the molecularweight, alkali solubility necessary for development is maintained, andincreasing the molecular weight is advantageous in terms of increasingthe elongation of a cured film.

In addition, when the phenolic resin has an electron-withdrawing groupas R₁, a cured relief pattern profile is improved. Although not wishingto be bound by a mechanism, this is presumed to be caused because R₁ isa group having polarity and exhibits a strong interaction with thephenolic hydroxyl group in the resin. The softening point of the resinrises due to the interaction, so that when the relief pattern afterdevelopment is heated to form a cured relief pattern, the patternprofile can be kept in a good state without losing the shape of reliefpattern.

In the case where m₂ is 2, the plurality of R₁ may be the same as ordifferent from each other.

When m₁ is 1, m₂ is preferably from 1 to 2, and R₁ is preferably anelectron-withdrawing group.

Among the groups described above, in view of less production of aby-product during the polymer synthesis, R₁ is more preferably amonovalent group represented by following formula (5):

{in formula (5), R₁₅ is a monovalent group selected from the groupconsisting of a hydroxyl group, —NH₂, and groups represented by —NH—R₁₉,—N(R₁₉)₂ and —O—R₁₉ (wherein R₁₉ is a monovalent group selected from analiphatic group having a carbon number of 1 to 12, an alicyclic grouphaving a carbon number of 3 to 12, and an aromatic group having a carbonnumber of 6 to 18)}.

Furthermore, from the standpoint that the alkali solubility is easilycontrolled, R₁₅ is more preferably a group represented by —O—R₁₉.

In formula (1), R₂ to R₅ are not limited as long as each isindependently a hydrogen atom, a monovalent aliphatic group having acarbon number of 1 to 10, or a monovalent aliphatic group having acarbon number of 1 to 10, in which some hydrogen atoms or all hydrogenatoms are substituted with a fluorine atom. Among others, in view ofsensitivity of the photosensitive resin composition formed, each of R₂to R₅ is independently, preferably a hydrogen atom or a monovalentaliphatic group having a carbon number of 1 to 3, and in view of heatresistance, it is more preferred that all of R₂ to R₅ are a hydrogenatom.

In formula (1), each of R₆ and R₇ is independently a halogen atom, ahydroxyl group or a monovalent organic group. Among others, in view ofheat resistance, each of R₆ and R₇ is preferably a hydroxyl group or analiphatic group having a carbon number of 1 to 3.

In formula (1), each of m₃ and m₄ is independently an integer of 0 to 4.In view of heat resistance, it is preferable that m₃ and m₄ are 0.

W in formula (1) is described below.

W is a divalent group selected from the group consisting of a singlebond, a chain aliphatic group having a carbon number of 1 to 10, a chainaliphatic group having a carbon number of 1 to 10, in which somehydrogen atoms or all hydrogen atoms are substituted with a fluorineatom, an alicyclic group having a carbon number of 3 to 20, an alicyclicgroup having a carbon number of 3 to 20, in which some hydrogen atoms orall hydrogen atoms are substituted with a fluorine atom, an alkyleneoxide group having from 1 to 20 repeating units, and groups representedby following formula (2):

In view of heat resistance of the resin, W is preferably a single bondor a divalent group represented by formula (2), more preferably a singlebond.

In formula (1), Y is not limited as long as it is a structurerepresented by formula (3) or (4).

In formula (3), R₈ and R₉ are not limited as long as they are a hydrogenatom or a monovalent organic group having a carbon number of 1 to 11,and in view of heat resistance of the cured film, they are preferably agroup selected from a hydrogen atom, a hydrocarbon group having a carbonnumber of 1 to 3, a monovalent organic group having a carbon number of 1to 11 and containing a polymerizable group, such as double bond, and amonovalent organic group having a carbon number of 1 to 11 andcontaining a polar group, such as hydroxyl group or carboxyl group.

Furthermore, in view of sensitivity of the photosensitive resincomposition formed, R₈ and R₉ are more preferably a group selected froma hydrogen atom and a hydrocarbon group having a carbon number of 1 to3.

In formula (4), each of R₁₁ to R₁₄ is independently a hydrogen atom, amonovalent aliphatic group having a carbon number of 1 to 10, or amonovalent aliphatic group having a carbon number of 1 to 10, in whichsome hydrogen atoms or all hydrogen atoms are substituted with afluorine atom.

In view of heat resistance, R₁₁ to R₁₄ are preferably a monovalentaliphatic group having a carbon number of 1 to 3, or a hydrogen atom,and in view of sensitivity of the photosensitive resin compositionformed, they are more preferably a hydrogen atom.

In formula (4), m₅ is an integer of 1 to 4, and when m₅ is 1, R₁₂ is notlimited as long as it is a hydroxyl group, a carboxyl group or asulfonic acid group.

When m₅ is an integer of 2 to 4, at least one R₁₂ is a hydroxyl groupand the remaining R₁₂ are a halogen atom, a hydroxyl group, a monovalentorganic group, a carboxyl group or a sulfonic acid group. All of R₁₀ maybe the same or different.

Among others, in view of heat resistance, the divalent organic grouprepresented by formula (4) preferably has a structure represented byfollowing formula (20), and in view of sensitivity, and more preferablyhas a structure represented by following formula (12):

(in formulae (20) and (12), R₁₇ is a hydrocarbon group having a carbonnumber of 1 to 10 or an alkoxy group having a carbon number of 1 to 10;m₆ is an integer of 0 to 3, and when m₆ is 2 or 3, the plurality of R₁₇may be the same or different; and m₇ is an integer of 1 to 3; providedthat m₆ and m₇ satisfy 1≦(m₆+m₇)≦4).

Each of n₁ and n₂ in formula (1) indicates the total number of repeatingunits in the polymer main chain and is an integer of 1 to 500. In viewof toughness of the film cured, n₁ and n₂ are preferably 1 or more, andin view of solubility in an aqueous alkali solution, are preferably 500or less. The lower limit of n₁ and n₂ is preferably 2, more preferably3, and the upper limit of n₁ and n₂ is preferably 450, more preferably400, still more preferably 350.

By adjusting the ratio between n₁ and n₂, a photosensitive resincomposition having more preferable film properties and more improvedalkali solubility can be prepared. As the value of n₁/(n₁+n₂) is larger,the film properties after curing are better and the heat resistance ismore excellent, whereas as the value of n₁/(n₁+n₂) is smaller, thealkali solubility is more improved and the pattern profile after curingis more excellent. Although not wishing to be bound by a mechanism,these results are presumed to occur because as the value of n₁/(n₁+n₂)in formula (1) is larger, the average distance between crosslinkingpoints of the phenolic resin as a heat-curable resin is longer.Accordingly, when m₁ is 2 or 3, the value of n₁/(n₁+n₂) is preferablyn₁/(n₁+n₂)=0.05 to 0.95 in view of film properties after curing, morepreferably n₁/(n₁+n₂)=0.35 to 0.9 in view of film properties aftercuring and alkali solubility, still more preferably n₁/(n₁+n₂)=0.4 to0.8 in view of film properties after curing, pattern profile and alkalisolubility. Although not wishing to be bound by a mechanism, it isbelieved that by forming the resin as a copolymer, the amount of a lowmolecular weight component having a novolak structure probably greatlycontributing to weight loss during heat curing is reduced, and theresidual film ratio during heat curing is increased.

In addition, when m₁ is 1, n₁/(n₁+n₂) is from 0.35 to 0.9. Among others,in view of film properties after curing, pattern profile and alkalisolubility, n₁/(n₁+n₂) is preferably from 0.4 to 0.8. In addition, whenm₁ is 1, in view of pattern profile and alkali solubility, it ispreferable that m₂ is 1 or 2 and R₁ is an electron-withdrawing group.

The structure of resin (A-1) may be a block structure or a randomstructure, and is preferably a block structure in light of adhesivenessto a substrate.

Among others, in view of elongation and heat resistance, the structureof resin (A-1) is preferably a structure represented by followingformula (13):

{in formula (13), each m₂ is independently an integer of 0 to 2; each ofm₃ and m₄ is independently an integer of 0 to 4; each of n₁ and n₂ isindependently an integer of 1 to 500, and n₁/(n₁+n₂) is from 0.35 to0.8; each R₁ is independently a monovalent group having a carbon numberof 1 to 10 selected from a hydrocarbon group and an alkoxy group; whenm₂ is 2, the plurality of R₁ may be the same as or different from eachother; each of R₂ to R₅ is independently a hydrogen atom, a monovalentaliphatic group having a carbon number of 1 to 10, or a monovalentaliphatic group having a carbon number of 1 to 10, in which somehydrogen atoms or all hydrogen atoms are substituted with a fluorineatom; each of R₆ and R₇ is independently a halogen atom, a hydroxylgroup or a monovalent organic group; when m₃ is from 2 to 4, theplurality of R₆ may be the same as or different from each other; when m₄is an integer of 2 to 4, the plurality of R₇ may be the same as ordifferent from each other; Y is a methylene group or a structurerepresented by following formula (14); and the polymer structure may bea random structure or a block structure};

[Resin Mixture (A-2)]

In the embodiment, resin mixture (A-2) is a resin mixture including aresin containing a structure represented by following formula (7) and aresin containing a structure represented by following formula (8):

{in formulae (7) and (8), each X is independently a monovalent groupselected from the group consisting of a hydrogen atom, an alkoxycarbonylgroup having a carbon number of 2 to 20, an alkoxycarbonylmethyl grouphaving a carbon number of 2 to 20, an alkoxyalkyl group having a carbonnumber of 2 to 20, a silyl group substituted with at least one alkylgroup having a carbon number of 1 to 10, a tetrahydropyranyl group, anda tetrahydrofuranyl group; each m₁ is independently an integer of 1 to3, provided that the plurality of m₁ are not 1 at the same time, each m₂is independently an integer of 0 to 2, and 2≦(m₁+m₂)≦4; each of m₃ andm₄ is independently an integer of 0 to 4; each of n₁ and n₂ isindependently an integer of 1 to 500; each R₁ is independently amonovalent group selected from the group consisting of a hydrocarbongroup having a carbon number of 1 to 10, an alkoxy group having a carbonnumber of 1 to 10, a nitro group, a cyano group, and a group representedby following formula (5) or (6); when m₂ is 2, the plurality of R₁ maybe the same as or different from each other; each of R₂ to R₅ isindependently a hydrogen atom, a monovalent aliphatic group having acarbon number of 1 to 10, or a monovalent aliphatic group having acarbon number of 1 to 10, in which some hydrogen atoms or all hydrogenatoms are substituted with a fluorine atom; each of R₆ and R₇ isindependently a halogen atom, a hydroxyl group or a monovalent organicgroup; when m₃ is an integer of 2 to 4, the plurality of R₆ may be thesame as or different from each other; when m₄ is an integer of 2 to 4,the plurality of R₇ may be the same as or different from each other; Yis a divalent organic group represented by following formula (3) or (4);W is a divalent group selected from the group consisting of a singlebond, a chain aliphatic group having a carbon number of 1 to 10, a chainaliphatic group having a carbon number of 1 to 10, in which somehydrogen atoms or all hydrogen atoms are substituted with a fluorineatom, an alicyclic group having a carbon number of 3 to 20, an alicyclicgroup having a carbon number of 3 to 20, in which some, hydrogen atomsor all hydrogen atoms are substituted with a fluorine atom, an alkyleneoxide group having from 1 to 20 repeating units, and groups representedby following formula (2):

(wherein each of R₈ and R₉ is independently a hydrogen atom, amonovalent organic group having a carbon number of 1 to 11, or a groupcontaining a carboxyl group, a sulfonic acid group or a phenolichydroxyl group);

{in formula (4), each of R₁₁ to R₁₄ is independently a hydrogen atom, amonovalent aliphatic group having a carbon number of 1 to 10, or amonovalent aliphatic group having a carbon number of 1 to 10, in whichsome hydrogen atoms or all hydrogen atoms are substituted with afluorine atom; m₅ is an integer of 1 to 4; when m₅ is 1, R₁₀ is ahydroxyl group; when n₅ is an integer of 2 to 4, at least one R₁₀ is ahydroxyl group and the remaining R₁₀ are a halogen atom, a hydroxylgroup, or a monovalent organic group; and all R₁₀ may be the same ordifferent};

{in formula (5), R₁₅ is a monovalent group selected from the groupconsisting of a hydroxyl group, an aliphatic group having a carbonnumber of 1 to 12, an alicyclic group having a carbon number of 3 to 12,an aromatic group having a carbon number of 6 to 18, —NH₂, and groupsrepresented by —NH—R₁₉, —N(R₁₉)₂ and —O—R₁₉ (wherein R₁₉ is a monovalentgroup selected from an aliphatic group having a carbon number of 1 to12, an alicyclic group having a carbon number of 3 to 12, and anaromatic group having a carbon number of 6 to 18)};

{in formula (6), each of R₁₆ and R₁₇′ is independently a monovalentgroup selected from the group consisting of a hydrogen atom, analiphatic group having a carbon number of 1 to 12, an alicyclic grouphaving a carbon number of 3 to 12, and an aromatic group having a carbonnumber of 6 to 18, and R₁₆ and R₁₇′ may form a ring}.

In formulae (7) and (8), each X is independently a monovalent groupselected from the group consisting of a hydrogen atom, an alkoxycarbonylgroup having a carbon number of 2 to 20, an alkoxycarbonylmethyl grouphaving a carbon number of 2 to 20, an alkoxyalkyl group having a carbonnumber of 2 to 20, a silyl group substituted with at least one alkylgroup having a carbon number of 1 to 10, a tetrahydropyranyl group, anda tetrahydrofuranyl group. Among others, in view of sensitivity, X ispreferably a hydrogen atom, a tert-butoxycarbonyl group, atert-butoxycarbonylmethyl group, a tetrahydropyranyl group or atetrahydrofuranyl group, and in view of heat resistance, and is morepreferably a hydrogen atom.

In formulae (7) and (8), each m₁ is independently an integer of 1 to 3,provided that the plurality of m₁ are not 1 at the same time. In view ofalkali solubility and profile of the relief pattern cured, m₁ ispreferably 2 or 3, and in view of lithography, m₁ is more preferably 2.In order to facilitate interaction of the phenolic resin with photoacidgenerator (B), when m₁ is 2, the bonding-position relationship betweenhydroxyl groups in formula (1) is preferably the meta-position.

Preferable ranges or embodiments of m₂ to m₄, R₁ to R₅ and W in formulae(7) and (8) are the same as in formula (1).

In resin mixture (A-2), the weight ratio between the resin containing astructure represented by formula (7) and the resin containing astructure represented by formula (8) is preferably from 5:95 to 95:5,more preferably from 35:65 to 90:10 in light of film properties aftercuring and alkali solubility, still more preferably from 40:60 to 80:20in light of film properties after curing, pattern profile and alkalisolubility.

In view of heat resistance and lithography performance, the resinmixture containing structures represented by formulae (7) and (8) ispreferably a resin mixture containing structures represented byfollowing formula (15) and following formula (8a):

{in formulae (15) and (8a), m₁ is from 1 to 3; each m₂ is independentlyan integer of 0 to 2; each of m₃ and m₄ is independently an integer of 0to 4; each of n₁ and n₂ is independently an integer of 1 to 500; each R₁is independently a monovalent group having a carbon number of 1 to 10selected from a hydrocarbon group and an alkoxy group; when m₂ is 2, theplurality of R₁ may be the same as or different from each other; each R₂to R₅ is independently a hydrogen atom, a monovalent aliphatic grouphaving a carbon number of 1 to 10, or a monovalent aliphatic grouphaving a carbon number of 1 to 10, in which some hydrogen atoms or allhydrogen atoms are substituted with a fluorine atom; each of R₆ and R₇is independently a halogen atom, a hydroxyl group or a monovalentorganic group; when m₃ is from 2 to 4, the plurality of R₆ may be thesame as or different from each other; when m₄ is an integer of 2 to 4,the plurality of R₇ may be the same as or different from each other; Yis a methylene group or a structure represented by following formula(16); and the weight ratio of the resins containing structuresrepresented by formulae (15) and (8a) is from 35:65 to 80:20}:

In the embodiment, resin mixture (A-2) is a resin mixture including aresin containing a structure represented by following formula (9) and aresin containing a structure represented by following formula (10):

{in formulae (9) and (10), each X is independently a monovalent groupselected from the group consisting of a hydrogen atom, an alkoxycarbonylgroup having a carbon number of 2 to 20, an alkoxycarbonylmethyl grouphaving a carbon number of 2 to 20, an alkoxyalkyl group having a carbonnumber of 2 to 20, a silyl group substituted with at least one alkylgroup having a carbon number of 1 to 10, a tetrahydropyranyl group, anda tetrahydrofuranyl group; each m₂ is independently an integer of 0 to2, provided that the plurality of m₂ are not 0 at the same time; each ofn₁ and n₂ is independently an integer of 1 to 500; each R₁ isindependently a monovalent group selected from the group consisting of anitro group, a cyano group, a group represented by formula (5), and agroup represented by formula (6); when m₂ is 2, the plurality of R₁ maybe the same as or different from each other; each of R₂ to R₅ isindependently a hydrogen atom, a monovalent aliphatic group having acarbon number of 1 to 10, or a monovalent aliphatic group having acarbon number of 1 to 10, in which some hydrogen atoms or all hydrogenatoms are substituted with a fluorine atom; each of R₆ and R₇ isindependently a halogen atom, a hydroxyl group or a monovalent organicgroup; when m₃ is an integer of 2 to 4, the plurality of R₆ may be thesame as or different from each other; when m₄ is an integer of 2 to 4,the plurality of R₇ may be the same as or different from each other; Yis a divalent organic group represented by formula (3) or (4); W is adivalent group selected from the group consisting of a single bond, achain aliphatic group having a carbon number of 1 to 10, a chainaliphatic group having a carbon number of 1 to 10, in which somehydrogen atoms or all hydrogen atoms are substituted with a fluorineatom, an alicyclic group having a carbon number of 3 to 20, an alicyclicgroup having a carbon number of 3 to 20, in which some hydrogen atoms orall hydrogen atoms are substituted with a fluorine atom, an alkyleneoxide group having from 1 to 20 repeating units, and groups representedby following formula (2):

and the weight ratio between the resin containing the structurerepresented by formula (9) and the resin containing the structurerepresented by formula (10) is from 5:95 to 95:5}.

In formulae (9) and (10), each X is independently a monovalent groupselected from the group consisting of a hydrogen atom, an alkoxycarbonylgroup having a carbon number of 2 to 20, an alkoxycarbonylmethyl grouphaving a carbon number of 2 to 20, an alkoxyalkyl group having a carbonnumber of 2 to 20, a silyl group substituted with at least one alkylgroup having a carbon number of 1 to 10, a tetrahydropyranyl group, anda tetrahydrofuranyl group. In view of sensitivity, X is preferably ahydrogen atom, a tert-butoxycarbonyl group, a tert-butoxycarbonylmethylgroup, a tetrahydropyranyl group, or a tetrahydrofuranyl group, and inview of heat resistance, more preferably a hydrogen atom.

In formulae (9) and (10), the value of m₂ is preferably 1 in light ofreactivity during the polymer synthesis.

Preferable ranges or embodiments of m₃, m₄, R₁ to R₇, W and Y in formula(9) and (10) are the same as in formula (1).

The weight ratio between the resin containing a structure represented byformula (9) and the resin containing a structure represented by formula(10) is from 5:95 to 95:5, preferably from 35:65 to 90:10 in light offilm properties after curing and alkali solubility, more preferably from40:60 to 80:20 in light of film properties after curing, pattern profileand alkali solubility.

The resin containing a structure represented by formula (1), (7), (8),(9), (10), (13) or (15) is not limited as long as it has the structurerepresented by the formula above in the resin structure. The structureof the resin may be a phenolic resin structure alone or a copolymer witha resin, such as alkali-soluble polyimide, polyimide precursor,polybenzoxazole precursor, polyhydroxystyrene, etc. In view oftransparency of the resin, the structure is preferably a phenolic resinalone.

In the embodiment of the present invention, the resin containing astructure represented by following formula (17) or (18) can be alsoprovided by itself or in the form of a photosensitive resin composition:

{in formula (17), each of R₁ and R₁₇ is independently a monovalent grouphaving a carbon number of 1 to 10 selected from a hydrocarbon group andan alkoxy group; m₁ is an integer of 2 or 3; each of m₂ and m₆ isindependently an integer of 0 to 2, and 2≦m₁+m₂≦4; each of n₁ and n₂ isindependently an integer of 1 to 500 and satisfies 0.05≦n₁/(n₁+n₂)≦1;when m₂ is 2, the plurality of R₁ may be the same or different; and thepolymer structure may be a random structure or a block structure};

{in formula (18), each R₁ is independently a monovalent group having acarbon number of 1 to 10 selected from a hydrocarbon group and an alkoxygroup; m₁ is an integer of 2 or 3, m₂ is an integer of 0 to 2, each ofn₁ and n₂ is independently an integer of 1 to 500, and m₁, m₂, n₁ and n₂satisfy 2≦m₁+m₂≦4 and 0.35≦n₁/(n₁+n₂)≦0.95; when m₂ is 2, the pluralityof R₁ may be the same or different; and the polymer structure may be arandom structure or a block structure}.

In formula (17), m₁ is not limited as long as it is an integer of 2 or3. Among others, in view of lithography performance, m₁ is preferably 2.

In formula (17), R₁ and R₁₇ are not limited as long as each isindependently a group having a carbon number of 1 to 10 selected from ahydrocarbon group and an alkoxy group. In view of heat resistance, eachis preferably a hydrocarbon group having a carbon number of 1 to 3.

In formula (17), m₂ and m₆ are not limited as long as each isindependently an integer of 0 to 2. Among others, in view of heatresistance, m₂ is preferably 0, and m₆ is preferably 0 or 1.

In formula (17), n₁ and n₂ are not limited as long as each isindependently an integer of 1 to 500 and satisfies 0.05≦n₁/(n₁+n₂)≦1. Inview of light of film properties, 0.35≦n₁/(n₁+n₂)≦0.9 is preferableafter curing and alkali solubility, and 0.4≦n₁/(n₁+n₂)≦0.8 is morepreferred in light of film properties after curing, pattern profile andalkali solubility.

In a case of 0.9<n₁/(n₁+n₂)≦1, m₂ is preferably 1, and R₁ is preferablyan electron-withdrawing group.

In formula (18), m₁ is not limited as long as it is an integer of 2 or3. In view of lithography performance, m₁ is preferably 2.

In formula (18), R₁ is not limited as long as each of R₁ isindependently a group having a carbon number of 1 to 10 selected from ahydrocarbon group and an alkoxy group. Among others, in view of heatresistance, each of R₁ is preferably a hydrocarbon group having a carbonnumber of 1 to 3.

In formula (17), the value of m₂ is not limited as long as it is aninteger of 0 to 2. In view of heat resistance, m₂ is preferably 0.

In formula (18), n₁ and n₂ are not limited as long as each isindependently an integer of 1 to 500 and satisfies 0.35≦n₁/(n₁+n₂)≦0.95.In view of light of film properties, 0.4≦n₁/(n₁+n₂)≦0.8 is preferredafter curing, pattern profile and alkali solubility.

In the embodiment, a resin containing a structure represented byfollowing formula (19) may also be used as resin (A-1):

{in formula (19), each X is independently a monovalent group selectedfrom the group consisting of a hydrogen atom, an alkoxycarbonyl grouphaving a carbon number of 2 to 20, an alkoxycarbonylmethyl group havinga carbon number of 2 to 20, an alkoxyalkyl group having a carbon numberof 2 to 20, a silyl group substituted with at least one alkyl grouphaving a carbon number of 1 to 10, a tetrahydropyranyl group, and atetrahydrofuranyl group; each m₁ is independently an integer of 1 to 3,each m₂ is independently an integer of 1 to 2, and 2≦(m₁+m₂)≦4; each ofn₁ and n₂ is independently an integer of 1 to 500, and n₁/(n₁+n₂) isfrom 0.05 to 1; each R₁ is independently a monovalent group selectedfrom the group consisting of a nitro group, a cyano group, a grouprepresented by formula (5), and a group represented by formula (6); whenm₂ is 2, the plurality of R₁ may be the same as or different from eachother; m₇ is an integer of 0 to 2; R₁₈ is a hydroxyl group or a methylgroup; when m₇=2, the plurality of R₁₈ may be the same as or differentfrom each other; z is an integer of 0 or 1; Y is a methylene group or astructure represented by formula (16); and the polymer structure may bea random structure or a block structure).

In view of sensitivity, X is preferably a hydrogen atom, atert-butoxycarbonyl group, a tert-butoxycarbonylmethyl group, atetrahydropyranyl group, or a tetrahydropyranyl group, and in view ofheat resistance, is more preferably a hydrogen atom.

R₁ is not limited as long as it is a monovalent group selected from anitro group, a cyano group, a group represented by formula (5), and agroup represented by formula (6). From the standpoint that littleby-product is produced during the polymer synthesis, R₁ is preferably amonovalent group represented by formula (5).

Furthermore, from the standpoint that the alkali solubility is easilycontrolled, R₁₅ is more preferably a group represented by —O—R₁₉.

m₁ is not limited as long as it is an integer of 1 to 3. Among others,in view of alkali solubility and cured relief pattern profile, inparticular, in view of lithography, m₁ is preferably 2 or 3.

m₂ is not limited as long as it is an integer of 1 to 2. Among others,in view of reactivity in the polymer synthesis, m₂ is preferably 1.

z is not limited as long as it is an integer of 0 or 1. In view ofelongation, z is preferably 1.

Typically, the resin constituting resin (A-1) or resin mixture (A-2) canbe synthesized by polymerization reaction of a phenolic compound and apolymerization component. Specifically, the polymerization componentincludes a component containing one or more kinds of compounds selectedfrom the group consisting of a compound having two methylol groups inthe molecule, a compound having two alkoxymethyl groups in the molecule,a compound having two haloalkyl groups in the molecule, and a compoundhaving an aldehyde group. More typically, the polymerization componentis preferably a component consisting of at least one compound thereof.For example, a phenolic compound is subjected to a polymerizationreaction with one or more kinds of compounds selected from the groupconsisting of a compound having two methylol groups in the molecule, acompound having two alkoxymethyl groups in the molecule, a compoundhaving two haloalkyl groups in the molecule, and a compound having analdehyde group, whereby phenolic resin (A-1) can be obtained. In view ofreaction control and stability of phenolic resin (A-1) andphotosensitive resin composition obtained, the molar ratio between thephenolic compound charged and the polymerization component charged ispreferably from 5:1 to 1.01:1, more preferably from 2.5:1 to 1.1:1.

In the embodiment, the phenolic compound used for the synthesis of theresin constituting resin (A-1) or resin mixture (A-2) is described. Thephenolic compound includes monohydric to trihydric phenols and ispreferably a dihydric phenol or a trihydric phenol.

In the description of the present invention, the monohydric phenolindicates a compound in which one hydroxyl group is bonded directly to abenzene ring. Specifically, the monohydric phenol includes, for example,phenol and a phenol in which a hydrogen atom on an aromatic ring issubstituted with an alkyl or alkoxy group having a carbon number of 1 to10, and in view of thermal expansion coefficient after curing, phenol orcresol is preferred.

In the description of the present invention, the dihydric phenolindicates a compound in which two hydroxyl groups are bonded directed toa benzene ring. Specifically, the dihydric phenol includes, for example,resorcin, hydroquinone, catechol, etc. One of these dihydric phenols maybe used alone, or two or more thereof may be used in combination. Inview of alkali solubility and interaction with diazonaphthoquinone,resorcin is preferred.

Furthermore, the dihydric phenol may be a compound in which a hydrogenatom on an aromatic ring is substituted for by an alkyl or alkoxy grouphaving a carbon number of 1 to 10, and in view of thermal expansioncoefficient after curing, an unsubstituted dihydric phenol is preferred.

In the description of the present invention, the trihydric phenolindicates a compound in which three hydroxyl groups are bonded directlyto a benzene ring. Specifically, the trihydric phenol includes, forexample, pyrogallol, phloroglucinol, 1,2,4-trihydroxybenzene, etc. Oneof these trihydric phenols may be used alone, or two or more thereof maybe used in combination. In view of lithography performance, pyrogallolis preferred.

Furthermore, the trihydric phenol may be a compound in which a hydrogenatom on an aromatic ring is substituted with an alkyl or alkoxy grouphaving a carbon number of 1 to 10, and in view of thermal expansioncoefficient after curing, an unsubstituted trihydric phenol ispreferable.

In the case where R₁ in formula (1) is an electron-withdrawing group,the electron-withdrawing group is not limited as long as it is a nitrogroup, a cyano group, or a structure represented by following formula(5) or (6):

{in formula (5), R₁₅ is a monovalent group selected from the groupconsisting of a hydroxyl group, an aliphatic group having a carbonnumber of 1 to 12, an alicyclic group having a carbon number of 3 to 12,an aromatic group having a carbon number of 6 to 18, —NH₂, and groupsrepresented by —NH—R₁₉, —N(R₁₉)₂ and —O—R₁₉ (wherein R₁₉ is a monovalentgroup selected from an aliphatic group having a carbon number of 1 to12, an alicyclic group having a carbon number of 3 to 12, and anaromatic group having a carbon number of 6 to 18)};

{in formula (6), each of R₁₆ and R₁₇′ is independently a monovalentgroup selected from the group consisting of a hydrogen atom, analiphatic group having a carbon number of 1 to 12, an alicyclic grouphaving a carbon number of 3 to 12, and an aromatic group having a carbonnumber of 6 to 18, and R₁₆ and R₁₇′ may form a ring}.

Among others, from the standpoint that a by-product is little producedduring the polymer synthesis, R₁₅ is preferably a monovalent groupselected from the group consisting of a hydroxyl group, —NH₂, and groupsrepresented by —NH—R₁₉, —N(R₁₉)₂ and —O—R₁₉, wherein R₁₉ is a monovalentgroup selected from an aliphatic group having a carbon number of 1 to12, an alicyclic group having a carbon number of 3 to 12, and anaromatic group having a carbon number of 6 to 18.

From the standpoint that the alkali solubility is also easilycontrolled, R₁₅ is more preferably a monovalent group selected from thegroup consisting of groups represented by —O—R₁₉, wherein R₁₉ is amonovalent group selected from an aliphatic group having a carbon numberof 1 to 12, an alicyclic group having a carbon number of 3 to 12, and anaromatic group having a carbon number of 6 to 18.

The phenolic compound used for the synthesis of the above-describedphenolic resin includes the following.

When R₁ is a nitro group, the phenolic compound includes 2-nitrophenol,3-nitrophenol, 4-nitrophenol, 4-nitrocatechol, 2-nitroresorcinol, etc.

When R₁ is a cyano group the phenolic compound includes 2-cyanophenol,3-cyanophenol, 4-cyanophenol, 4-cyanocatechol, etc.

In the case where R₁ is represented by formula (5), specific examples ofthe phenolic compound in which the number m₁ of phenolic hydroxyl groupsis 1 include 2-hydroxybenzoic acid, 3-hydroxybenzoic acid,4-hydroxybenzoic acid, 3-hydroxy-2-methylbenzoic acid,3-hydroxy-4-methylbenzoic acid, 4-hydroxy-2-methylbenzoic acid,4-hydroxy-3-methylbenzoic acid, 4-hydroxy-3,5-dimethylbenzoic acid,4-hydroxyisophthalic acid, 5-hydroxyisophthalic acid, methyl2-hydroxybenzoate, methyl 3-hydroxybenzoate, methyl 4-hydroxybenzoate,methyl 2-hydroxy-4-methylbenzoate, methyl 2-hydroxy-5-methylbenzoate,ethyl 2-hydroxybenzoate, ethyl 3-hydroxybenzoate, ethyl4-hydroxybenzoate, ethyl 2-hydroxy-6-methylbenzoate, propyl2-hydroxybenzoate, isopropyl 2-hydroxybenzoate, propyl4-hydroxybenzoate, isopropyl 4-hydroxybenzoate, butyl 2-hydroxybenzoate,isobutyl 2-hydroxybenzoate, butyl 4-hydroxybenzoate, sec-butyl4-hydroxybenzoate, isobutyl 4-hydroxybenzoate, isoamyl2-hydroxybenzoate, amyl 4-hydroxybenzoate, isoamyl 4-hydroxybenzoate,hexyl 4-hydroxybenzoate, heptyl 4-hydroxybenzoate, 2-ethylhexylsalicylate, 2-ethylhexyl 4-hydroxybenzoate, nonyl 4-hydroxybenzoate,dodecyl 4-hydroxybenzoate, 3,3,5-trimethylcyclohexyl salicylate, benzyl2-hydroxybenzoate, benzyl 4-hydroxybenzoate, 2-hydroxybenzamide,4-hydroxybenzamide, 2-hydroxyacetophenone, 4-hydroxyacetophenone,2-hydroxy-5-methylacetophenone, 4-hydroxy-3-methylacetophenone,2-hydroxypropiophenone, 4-hydroxypropiophenone, 2-hydroxybenzophenone,4-hydroxybenzophenone, 2-hydroxy-5-methylbenzophenone, etc.

In the case where R₁ is represented by formula (5), specific examples ofthe phenolic compound in which the number m₁ of phenolic hydroxyl groupsis 2 include 2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid,2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid,3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid,2,6-dihydroxy-4-methylbenzoic acid, 2,5-dihydroxyterephthalic acid,methyl 2,3-dihydroxybenzoate, methyl 2,4-dihydroxybenzoate, methyl2,5-dihydroxybenzoate, methyl 2,6-dihydroxybenzoate, methyl3,4-dihydroxybenzoate, methyl 3,5-dihydroxybenzoate, ethyl3,4-dihydroxybenzoate, ethyl 2,4-dihydroxy-6-methylbenzoate,2,4-dihydroxybenzamide, 3,5-dihydroxybenzamide,2,4-dihydroxyacetophenone, 2,5-dihydroxyacetophenone,2,6-dihydroxyacetophenone, 3,4-dihydroxyacetophenone,3,5-dihydroxyacetophenone, 2,4-dihydroxypropiophenone,2,4-dihydroxybenzophenone, 3,4-dihydroxybenzophenone, etc.

In the case where R₁ is represented by formula (5), specific examples ofthe phenolic compound in which the number m₁ of phenolic hydroxyl groupsis 3 include 2,3,4-trihydroxybenzoic acid, 2,4,6-trihydroxybenzoic acid,gallic acid (3,4,5-trihydroxybenzoic acid), methyl gallate, ethylgallate, propyl gallate, butyl gallate, isoamyl gallate, octyl gallate,dodecyl gallate, 2,3,4-trihydroxyacetophenone,2,4,6-trihydroxyacetophenone, 2,3,4-trihydroxybenzophenone, etc.

In the case where R₁ is represented by formula (6), specific examples ofthe phenolic compound includeN-(hydroxyphenyl)-5-norbornene-2,3-dicarboxyimide,N-(hydroxyphenyl)-5-methyl-5-norbornene-2,3-dicarboxyimide,N-(dihydroxyphenyl)-5-norbornene-2,3-dicarboxyimide,N-(dihydroxyphenyl)-5-methyl-5-norbornene-2,3-dicarboxyimide, etc.

In the case where R₁ is an electron-withdrawing group, m₂ in formula (1)is an integer of 1 to 3, and in view of reactivity in the polymersynthesis, is preferably 1 or 2, more preferably 1.

The polymerization component used for the synthesis of the resinconstituting resin (A-1) or resin mixture (A-2) is described below.

The compound having two methylol groups in the molecule includes, forexample, bis(hydroxymethyl)diphenyl ether,bis(hydroxymethyl)benzophenone, hydroxymethylphenylhydroxymethylbenzoate, bis(hydroxymethyl)biphenyl,dimethylbis(hydroxymethyl)biphenyl, etc. In view of reactivity andmechanical properties of phenolic resin (A-1) obtained, a compoundhaving a biphenyldiyl skeleton is preferred, and4,4′-bis(hydroxymethyl)biphenyl is more preferred.

The compound having two alkoxymethyl groups in the molecule includes,for example, bis(methoxymethyl)diphenyl ether,bis(methoxymethyl)benzophenone, methoxymethylphenylmethoxymethylbenzoate, bis(methoxymethyl)biphenyl,dimethylbis(methoxymethyl)biphenyl, etc. The carbon number of the alkoxymoiety in the alkoxymethyl group is, in view of reaction activity,preferably from 1 to 4, more preferably 1 or 2, and most preferably 1.

The compound having two haloalkyl groups in the molecule includes, forexample, bischloromethylbiphenyl, etc.

Specific examples of the compound having an aldehyde group includeformaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde,cyclopropanecarboxyaldehyde, pivalaldehyde, butylaldehyde,isobutylaldehyde, pentanal, 2-methylbutylaldehyde, isovaleraldehyde,hexanal, methylvaleraldehyde, 2-methylvaleraldehyde,2-ethylbutylaldehyde, 3,3-dimethylbutylaldehyde, cyclohexylaldehyde,heptanal, octanal, 2-ethylhexylaldehyde, nonanal,3,5,5-trimethylhexanaldehyde, decanal, undecanal, dodecanal, acrolein,crotonaldehyde, 3-methyl-2-butenal, tiglinaldehyde,3-cyclohexene-1-carboxyaldehyde, 2-nonenal, 10-undecenal,5-norbornenecarboxyaldehyde, perillaldehyde, citral, citronellal,benzaldehyde, ortho-tolualdehyde, meta-tolualdehyde, para-tolualdehyde,phenylacetaldehyde, diphenylacetaldehyde, naphthaldehyde, cinnamaldehydeglycolaldehyde, lactaldehyde, salicylaldehyde, 5-methylsalicylaldehyde,3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 4-hydroxy-3,5-dimethylbenzaldehyde, 2,3-dihydroxybenzaldehyde,2,4-dihydroxybenzaldehyde, 2,5-dihydroxybenzaldehyde,3,4-dihydroxybenzaldehyde, 2,3,4-trihydroxybenzaldehyde,2,4,5-trihydroxybenzaldehyde, 2,4,6-trihydroxybenzaldehyde,3,4,5-trihydroxybenzaldehyde, vanillin, ethylvanillin,ortho-anisaldehyde, meta-anisaldehyde, para-anisaldehyde, furfural,hydroxymethylfurfural, glyoxylic acid, succinmonoaldehyde, traumatin,etc.

In view of heat resistance and synthesis control, the compound ispreferably formaldehyde, acetaldehyde, propionaldehyde, pivalaldehyde,butylaldehyde, isobutylaldehyde, 5-norbornene-2-carboxyaldehyde,perillaldehyde, salicylaldehyde, 5-methylsalicylaldehyde,3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, or4-hydroxy-3,5-dimethylbenzaldehyde.

In view of photosensitivity during pattern formation, the compound ismore preferably formaldehyde, acetaldehyde, propionaldehyde,pivalaldehyde, butylaldehyde, or isobutylaldehyde.

A typical synthesis method of the resin constituting phenolic resin(A-1) or resin mixture (A-2) is described in detail below. Theabove-described phenolic compound and the above-described polymerizationcomponent are heated and stirred in the presence of an appropriatepolymerization catalyst, whereby the resin constituting phenolic resin(A-1) or resin mixture (A-2) can be obtained. The polymerizationcatalyst is not particularly limited but includes, for example, anacidic catalyst, an alkaline catalyst, etc., with an acidic catalystbeing preferred. The acidic catalyst includes, for example, an inorganicacid, such as hydrochloric acid, sulfuric acid, phosphonic acid, etc.;an organic acid, such as methanesulfonic acid, p-toluenesulfonic acid,oxalic acid, etc.; a Lewis acid, such as boron trifluoride, anhydrousaluminum chloride, zinc chloride, etc.; and diethyl sulfate. The amountof the acidic catalyst used is preferably from 0.01 to 100 mol % basedon the molar number of methylol compound, alkoxymethyl compound orhaloalkyl compound. The alkaline catalyst includes, for example, lithiumhydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide,barium hydroxide, sodium carbonate, triethylamine, pyridine,4-N,N-dimethylaminopyridine, piperidine, piperazine,1,4-diazabicyclo[2.2.2]octane, 1,8-diazabicyclo[5.4.0]-7-undecene,1,5-diazabicyclo[4.3.0]-5-nonene, ammonia, hexamethylenetetramine, etc.The amount of the alkaline catalyst used is preferably from 0.01 to 100mol % based on the molar number of methylol compound, alkoxymethylcompound or haloalkyl compound.

If necessary, an organic solvent can be used, when carrying out thesynthesis reaction of the resin constituting resin (A-1) or resinmixture (A-2). Specific examples of the organic solvent which can beused include, although are not particularly limited to,bis(2-methoxyethyl)ether, methyl cellosolve, ethyl cellosolve,triethylene glycol monomethyl ether, propylene glycol monomethyl ether,propylene glycol monomethyl ether acetate, diethylene glycol dimethylether, dipropylene glycol dimethyl ether, cyclohexanone, cyclopentanone,toluene, xylene, γ-butyrolactone, N-methyl-2-pyrrolidone,tetrahydrofurfuryl alcohol, etc. The amount of the organic solvent usedis usually from 10 to 1,000 parts by mass, preferably from 20 to 500parts by mass, per 100 parts by mass as the total mass of raw materialscharged. In addition, in the synthesis reaction of phenolic resin (A-1),the reaction temperature is usually from 20 to 250° C., preferably from40 to 200° C., and the reaction time is usually from 1 to 20 hours.

The weight average molecular weight of the resin constituting resin(A-1) or resin mixture (A-2) is preferably from 2,000 to 200,000, morepreferably from 3,000 to 120,000, still more preferably from 4,000 to50,000. The weight average molecular weight is preferably 2,000 or morein light of elongation and is preferably 200,000 or less in light ofalkali solubility.

The weight average molecular weight is a value obtained in terms ofstandard polystyrene by using gel permeation chromatography(hereinafter, referred to as “GPC”).

As the method of substituting some hydrogen atoms or all hydrogen atomsof the phenolic hydroxyl group of the resin constituting resin (A-1) orresin mixture (A-2) with a protective group for the phenolic hydroxylgroup, conventionally known methods may be used (see T. W. Greene,“Productive Groups in Organic Synthesis”, John Wiley & Sons (1981)).

Resin (A-1) in which some hydrogen atoms or all hydrogen atoms of thehydroxyl group in the phenolic resin obtained above are substituted withthe protective group is used in combination with the later-describedphotoacid generator (B), and the protective group is desorbed due to anacid generated in the exposed area to increase the solubility in analkali solution, whereby a relief pattern can be formed.

The photosensitive resin composition may also further contain resinssoluble in an aqueous alkali solution, other than the resin constitutingresin (A-1) and resin mixture (A-2), as long as they do not adverselyaffect the effects of the present invention. The other resin soluble inan aqueous alkali solution specifically includes, for example, a novolakresin, a polyhydroxystyrene-based resin, polyamide, polyimide, andderivatives, precursors and copolymers of these resins.

Incidentally, in the case where the resin constituting resin (A-1) orresin mixture (A-2) is used by mixing it with the other resin soluble inan aqueous alkali solution, the content of the resin constituting resin(A-1) or resin mixture (A-2) in the mixed resin composition is, in viewof elongation, preferably 50 mass % or more, more preferably 60 mass %or more.

[Photoacid Generator (B)]

In the embodiment, the photosensitive resin composition is notparticularly limited as long as it is a composition capable of forming aresin pattern in response to an actinic ray (radiation) typified byultraviolet ray, electron beam, X-ray, etc., and the composition may bea photosensitive resin composition of either a negative type (thenon-irradiated area is dissolved out by development) or a positive type(the irradiated area is dissolved out by development).

In the case of using the photosensitive resin composition as anegative-type composition, the photoacid generator (B) is a compoundcapable of generating an acid upon irradiation with radiation, and theacid generated causes a crosslinking reaction between the resinconstituting resin (A-1) or resin mixture (A-2) and other components, sothat the crosslinking product can be insoluble in a developer. Thecompound includes, for example, the following compounds:

(i) Trichloromethyl-s-triazines

tris(2,4,6-trichloromethyl)-s-triazine,2-phenyl-bis(4,6-trichloromethyl)-s-triazine,2-(3-chlorophenyl)-bis(4,6-trichloromethyl)-s-triazine,2-(2-chlorophenyl)-bis(4,6-trichloromethyl)-s-triazine,2-(4-methoxyphenyl)-bis(4,6-trichloromethyl)-s-triazine,2-(3-methoxyphenyl)-bis(4,6-trichloromethyl)-s-triazine,2-(2-methoxyphenyl)-bis(4,6-trichloromethyl)-s-triazine,2-(4-methylthiophenyl)-bis(4,6-trichloromethyl)-s-triazine,2-(3-methylthiophenyl)bis(4,6-trichloromethyl)-s-triazine,2-(2-methylthiophenyl)-bis(4,6-trichloromethyl)-s-triazine,2-(4-methoxynaphthyl)-bis(4,6-trichloromethyl)-s-triazine,2-(3-methoxynaphthyl)-bis(4,6-trichloromethyl)-s-triazine,2-(2-methoxynaphthyl)-bis(4,6-trichloromethyl)-s-triazine,2-(3,4,5-trimethoxy-β-styryl)-bis(4,6-trichloromethyl)-s-triazine,2-(4-methylthio-(3-styryl)-bis(4,6-trichloromethyl)-s-triazine,2-(3-methylthio-β-styryl)-bis(4,6-trichloromethyl)-s-triazine,2-(2-methylthio-β-styryl)-bis(4,6-trichloromethyl)-s-triazine, etc.;

(ii) Diaryliodonium Salts

diphenyliodonium tetrafluoroborate, diphenyliodoniumtetrafluorophosphate, diphenyliodonium tetrafluoroarsenate,diphenyliodonium trifluoromethanesulfonate, diphenyliodoniumtrifluoroacetate, diphenyliodonium p-toluenesulfonate,4-methoxyphenylphenyliodonium tetrafluoroborate,4-methoxyphenylphenyliodonium hexafluorophosphonate,4-methoxyphenylphenyliodonium hexafluoroarsenate,4-methoxyphenylphenyliodonium trifluoromethanesulfonate,4-methoxyphenylphenyliodonium trifluoroacetate,4-methoxyphenylphenyliodonium p-toluenesulfonate,bis(4-ter-butylphenyl)iodonium tetrafluoroborate,bis(4-ter-butylphenyl)iodonium hexafluoroarsenate,bis(4-ter-butylphenyl)iodonium trifluoromethanesulfonate,bis(4-ter-butylphenyl)iodonium trifluoroacetate,bis(4-ter-butylphenyl)iodonium p-toluenesulfonate, etc.; and

(iii) Triarylsulfonium Salts

triphenylsulfonium tetrafluoroborate, triphenylsulfoniumhexafluorophosphonate, triphenylsulfonium hexafluoroarsenate,triphenylsulfonium methanesulfonate, triphenylsulfoniumtrifluoroacetate, triphenylsulfonium p-toluenesulfonate,4-methoxyphenyldiphenylsulfonium tetrafluoroborate,4-methoxyphenyldiphenylsulfonium hexafluorophosphonate,4-methoxyphenyldiphenylsulfonium hexafluoroarsenate,4-methoxyphenyldiphenylsulfonium methanesulfonate,4-methoxyphenyldiphenylsulfonium trifluoroacetate,4-methoxyphenyldiphenylsulfonium p-toluenesulfonate,4-phenylthiophenyldiphenyl tetrafluoroborate, 4-phenylthiophenyldiphenylhexafluorophosphonate, 4-phenylthiophenyldiphenyl hexafluoroarsenate,4-phenylthiophenyldiphenyl trifluoromethanesulfonate,4-phenylthiophenyldiphenyl trifluoroacetate,4-phenylthiophenyldiphenyl-p-toluenesulfonate, etc.

Among the compounds of (i) to (iii), preferabletrichloromethyl-s-triazines are2-(3-chlorophenyl)-bis(4,6-trichloromethyl)-s-triazine,2-(4-chlorophenyl)-bis(4,6-trichloromethyl)-s-triazine,2-(4-methylthiophenyl)-bis(4,6-trichloromethyl)-s-triazine,2-(4-methoxy-β-styryl)-bis(4,6-trichloromethyl)-s-triazine,2-(4-methoxynaphthyl)-bis(4,6-trichloromethyl)-s-triazine, etc.;preferable diaryliodonium salts are diphenyliodonium trifluoroacetate,diphenyliodonium trifluoromethanesulfonate,4-methoxyphenylphenyliodonium trifluoromethanesulfonate,4-methoxyphenylphenyliodonium trifluoroacetate, etc.; and preferabletriarylsulfonium salts are triphenylsulfonium methanesulfonate,triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfoniummethanesulfonate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate,4-phenylthiophenyldiphenyl trifluoromethanesulfonate,4-phenylthiophenyldiphenyl trifluoroacetate, etc.

Other than the compounds of (i) to (iii), the following compounds mayalso be used as photoacid generator (B):

(1) Diazo Ketone Compound

The diazo ketone compound includes, for example, a 1,3-diketo-2-diazocompound, a diazobenzoquinone compound, a diazonaphthoquinone compound,etc., and specific examples thereof include1,2-naphthoquinonediazide-4-sulfonate compounds of phenols.

(2) Sulfone Compound

The sulfone compound includes, for example, a β-ketosulf one compound, aβ-sulfonylsulfone compound, and an α-diazo compound thereof. Specificexamples thereof include 4-trisphenacylsulfone, mesitylphenacylsulfone,bis(phenacylsulfonyl)methane, etc.

(3) Sulfonic Acid Compound

The sulfonic acid compound includes, for example, alkylsulfonic acidesters, haloalkylsulfonic acid esters, arylsulfonic acid esters,iminosulfonates, etc. Specific preferable examples of the sulfonic acidcompound include benzoin tosylate, pyrogalloltristrifluoromethanesulfonate, o-nitrobenzyl trifluoromethanesulfonate,o-nitrobenzyl p-toluenesulfonate, etc.

(4) Sulfonimide Compound

The sulfonimide compound includes, for example,N-(trifluoromethylsulfonyloxy)succinimide,N-(trifluoromethylsulfonyloxy)phthalimide,N-(trifluoromethylsulfonyloxy)diphenylmaleimide,N-(trifluoromethylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide,N-(trifluoromethylsulfonyloxy)naphthylimide, etc.

(5) Oxime Ester Compound

The oxime ester compound specifically includes2-[2-(4-methylphenylsulfonyloxyimino)]-2,3-dihydrothiophen-3-ylidene]-2-(2-methylphenyl)acetonitrile(trade name: “IRGACURE PAG 121” produced by Ciba Specialty ChemicalsInc.),[2-(propylsulfonyloxyimino)-2,3-dihydrothiophen-3-ylidene]-2-(2-methylphenyl)acetonitrile(trade name: “IRGACURE PAG 103” produced by Ciba Specialty ChemicalsInc.),[2-(n-octanesulfonyloxyimino)-2,3-dihydrothiophen-3-ylidene]-2-(2-methylphenyl)acetonitrile(trade name: “IRGACURE PAG 108” produced by Ciba Specialty ChemicalsInc.), α-(n-octanesulfonyloxyimino)-4-methoxybenzylcyanide (trade name:“CGI 725” produced by Ciba Specialty Chemicals Inc.), etc.

(6) Diazomethane Compound

The diazomethane compound specifically includesbis(trifluoromethylsulfonyl)diazomethane,bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane,etc.

In view of sensitivity, among others, the oxime ester compound (5) isparticularly preferred.

In the case where the photosensitive resin composition containing theresin constituting resin (A-1) or resin mixture (A-2) is of a negativetype, the blending amount of photoacid generator (B) is preferably from0.1 to 50 parts by mass, more preferably from 1 to 40 parts by mass, per100 parts by mass of the resin constituting resin (A-1) or resin mixture(A-2). When the blending amount is 0.1 parts by mass or more, the effectof improving the sensitivity can be successfully obtained, and when theblending amount is 50 parts by mass or less, the mechanical propertiesof the cured film are advantageous.

In the case of using the photosensitive resin composition as apositive-type composition, photoacid generators described in (i) to(iii) and (1) to (6) and/or a quinonediazide compound are suitably used.Among these, a quinonediazide compound is preferred in view of physicalproperties after curing. This is because the quinonediazide compound isthermally decomposed during curing and the amount of the compoundremaining in the cured film is very small. The quinonediazide compoundincludes, for example, compounds having a 1,2-benzoquinonediazidestructure or a 1,2-naphthoquinonediazide structure (hereinafter,sometimes referred to as “NQD compound”). These compounds are describedin detail, for example, in U.S. Pat. Nos. 2,772,972, 2,797,213,3,669,658, etc. The NQD compound is at least one compound selected fromthe group consisting of a 1,2-naphthoquinonediazide-4-sulfonic acidester of a compound having a plurality of phenolic hydroxyl groups(hereinafter, sometimes referred to as “polyhydroxy compound”), which isdescribed in detail below, and a 1,2-naphthoquinonediazide-5-sulfonicacid ester of the polyhydroxy compound.

The NQD compound is obtained, in a conventional manner, by treating anaphthoquinonediazide sulfonic acid compound with chlorosulfonic acid,thionyl chloride, etc. to form a sulfonyl chloride, and reacting theobtained naphthoquinonediazide sulfonyl chloride with the polyhydroxycompound. For example, a predetermined amount of the polyhydroxycompound and a predetermined amount of1,2-naphthoquinonediazide-5-sulfonyl chloride or1,2-naphthoquinonediazide-4-sulfonyl chloride are reacted in a solvent,such as dioxane, acetone, tetrahydrofuran, etc., in the presence of abasic catalyst, such as triethylamine, to carry out esterification, andthe obtained product is washed with water and dried, whereby the NQDcompound can be obtained.

In view of physical properties of the cured film, such as sensitivityand elongation, the preferable NQD compound includes, for example,compounds represented by the following formula group:

{wherein Q is a hydrogen atom or a naphthoquinonediazide sulfonic acidester group represented by any one of the following formula group:

provided that all Q are not hydrogen atoms at the same time}.

In addition, as the NQD compound, a naphthoquinonediazide sulfonyl estercompound having a naphthoquinonediazide-4-sulfonyl group and anaphthoquinonediazide-5-sulfonyl group in the same molecule may also beused, or a mixture of a naphthoquinonediazide-4-sulfonyl ester compoundand a naphthoquinonediazide-5-sulfonyl ester compound may also be used.

As the NQD compound, one of the above compounds may be used alone, ortwo or more of the above compounds may be mixed and used.

In the case where the photosensitive resin composition is of a positivetype, the blending amount of photoacid generator (B) in thephotosensitive resin composition is from 0.1 to 70 parts by mass,preferably from 1 to 40 parts by mass, more preferably from 5 to 30parts by mass, per 100 parts by mass of the resin constituting resin(A-1) or resin mixture (A-2). When the blending amount is 0.1 parts bymass, good sensitivity is obtained, and when the blending amount is 70parts by mass or less, mechanical properties of the cured film areadvantageous.

[Crosslinking Agent (C)]

In the embodiment, in order to more improve the thermophysicalproperties and mechanical properties of the cured product, it ispreferable to further blend (C) a crosslinking agent in thephotosensitive resin composition.

As the crosslinking agent (C), a known crosslinking agent can be used,and examples thereof include, but are not limited to, an epoxy compound,an oxetane compound, an oxazoline compound, a carbodiimide compound,aldehyde, an aldehyde-modified product, an isocyanate compound, anunsaturated bond-containing compound, a melamine compound, a metalchelating agent, a methylol compound or alkoxymethyl compoundrepresented by following formula (21), an N-methylol compound orN-alkoxymethyl compound having a structure represented by followingformula (22), and a compound having a divalent group represented byfollowing formula (23).

Among these, in view of film properties after curing, an epoxy compound,an oxetane compound, an oxazoline compound, an isocyanate compound, amethylol compound or alkoxymethyl compound represented by followingformula (21), an N-methylol compound or N-alkoxymethyl compoundrepresented by following formula (22), a divalent group-containingcompound having a structure represented by following formula (23), etc.,are preferred, and in view of pattern profile after curing, an epoxycompound, an isocyanate compound, an N-methylol compound orN-alkoxymethyl compound having a structure represented by followingformula (22), etc., are more preferred:

{in formula (21), R₂₀ is a hydrogen atom or a monovalent group selectedfrom the group consisting of a methyl group, an ethyl group, an n-propylgroup and an isopropyl group; R₂₁ is at least one monovalent groupselected from the group consisting of a hydroxyl group, and alkyl grouphaving a carbon number of 1 to 10, an alkoxy group, an ester group and aurethane group; m₈ is an integer of 1 to 5, and m₉ is an integer of 0 to4, provided that 1≦(m₈+m₉)≦5; n₃ is an integer of 1 to 4; V₁ is CH₂OR₂₀or R₂₁ when n₃=1, and is a single bond or a di- to tetravalent organicgroup when n₃=2 to 4; when a plurality of CH₂OR₂₀ are present, theplurality of R₂₀ may be the same as or different from each other; andwhen a plurality of R₂₁ are present, the plurality of R₂₁ may be thesame as or different from each other};

{in formula (22), each of R₂₂ and R₂₃ is independently a hydrogen atomor a hydrocarbon group having a carbon number of 1 to 10};

{in formula (23), R₂₄ is a functional group selected from the groupconsisting of a hydrogen atom, an alkyl group having a carbon number of1 to 6, and an alkenyl group having a carbon number of 1 to 6, V₂ is adivalent group selected from the group consisting of —CH₂—, —O— and —S—,V₃ is a divalent organic group, m₁₀ is an integer of 0 to 4, and when aplurality of R₂₄ are present, the plurality of R₂₄ may be the same as ordifferent from each other}.

Specific preferable examples of the epoxy compound include1,1,2,2-tetra(p-hydroxyphenyl)ethane tetraglycidyl ether, glyceroltriglycidyl ether, ortho-sec-butylphenyl glycidyl ether,1,6-bis(2,3-epoxypropoxy)naphthalene, diglycerol polyglycidyl ether,polyethylene glycol glycidyl ether, triglycidyl isocyanurate, EPICLON830, 850, 1050, N-680, N-690, N-695, N-770, HP-7200, HP-820 andEXA-4850-1000 (trade names, produced by DIC Corp.), and DENACOL EX-201,EX-313, EX-314, EX-321, EX-411, EX-511, EX-512, EX-612, EX-614, EX-614B,EX-731, EX-810, EX-911 and EM-150 (trade names, produced by NagaseChemteX Corporation). Among these, in view of elongation and heatresistance of the obtained heat-cured film, epoxy compounds of EPICLON830, 850, 1050, N-680, N-690, N-695, N-770, HP-7200, HP-820 andEXA-4850-1000, and DENACOL EX-201, EX-313, EX-314, EX-321, EX-411,EX-511, EX-512, EX-612, EX-614, EX-614B, EX-731, EX-810, EX-911 andEM-150 are preferred.

Specific preferable examples of the oxetane compound include xylylenebisoxetane, 3-ethyl-3{[(3-ethyloxetanyl)methoxy]methyl}oxetane,ETERNACOLL OXBP (trade name, produced by Ube Industries, Ltd.), etc.

Specific preferable examples of the oxazoline compound include2,2′-bis(2-oxazoline), 2,2′-isopropylidenebis(4-phenyl-2-oxazoline),1,3-bis(4,5-dihydro-2-oxazolyl)benzene,1,4-bis(4,5-dihydro-2-oxazolyl)benzene, EPOCROS K-2010E, K-2020E,K-2030E, WS-500, WS-700 and RPS-1005 (trade names, produced by NipponShokubai Co., Ltd.), etc. In view of elongation and heat resistance ofthe obtained heat-cured film, 1,3-bis(4,5-dihydro-2-oxazolyl)benzene ispreferred.

Specific preferable examples of the carbodiimide compound includeCARBODILITE SV-02, V-01, V-02, V-03, V-04, V-05, V-07, V-09, E-01, E-02and LA-1 (trade names, produced by Nisshinbo Chemical Inc.), etc.

Specific preferable examples of the isocyanate-based crosslinking agentinclude 4,4′-diphenylmethane diisocyanate, tolylene diisocyanate,1,3-phenylenebismethylene diisocyanate,dicyclohexylmethane-4,4′-diisocyanate, isophorone diisocyanate,hexamethylene diisocyanate, TAKENATE 500 and 600, COSMONATE NBDI and ND(trade names, produced by Mitsui Chemicals Inc.), DURANATE 17B-60PX,TPA-B80E, MF-B60X, MF-K60X and E402-B80T (trade names, produced by AsahiKasei Chemicals Corporation), etc.

Specific examples of the aldehyde and aldehyde-modified product (in thedescription of the present invention, the modified product indicates acompound capable of decomposing by means of heating to produce analdehyde) include formaldehyde, glutaraldehyde, hexamethylenetetramine,trioxane, glyoxal, malondialdehyde, succindialdehyde, etc.

Specific preferable examples of the melamine compound, the compoundrepresented by formula (21) and the compound represented by formula (22)include CYMEL 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141,272, 202, 1156, 1158, 1123, 1170 and 1174, UFR 65 and 300, MYCOAT 102and 105 (all produced by Mitsui Cytec Ltd.); NIKALAC MX-270, -280 and-290, NIKALAC MS-11, and NIKALAC MW-30, -100, -300, -390 and -750 (allproduced by Sanwa Chemical Co., Ltd.); DML-OCHP, DML-MBPC, DML-BPC,DML-PEP, DML-34X, DML-PSBP, DML-PTBP, DML-PCHP, DML-POP, DML-PFP,DML-MBOC, BisCMP-F, DML-BisOC-Z, DML-BisOCHP-Z, DML-BisOC-P, DMOM-PTBT,TMOM-BP, TMOM-BPA, and TML-BPAF-MF (all produced by Honshu ChemicalIndustry Co., Ltd.); benzenedimethanol, bis(hydroxymethyl)cresol,bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether,bis(hydroxymethyl)benzophenone, hydroxymethylphenylhydroxymethylbenzoate, bis(hydroxymethyl)biphenyl,dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene,bis(methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene,bis(methoxymethyl)diphenyl ether, bis(methoxymethyl)benzophenone,methoxymethylphenyl methoxymethylbenzoate, bis(methoxymethyl)biphenyl,dimethylbis(methoxymethyl)biphenyl, etc. Among these, in view ofelongation and heat resistance of the obtained heat-cured film, NIKALACMW-30MH, MW-100LH, BL-60, MX-270, MX-280 and MX-290, CYMEL 300, 303 and1123, MYCOAT 102 and 105, benzene dimethanol, TMOM-BP, TMOM-BPA,TML-BPAF-MF are preferred.

Specific preferable examples of the unsaturated bond-containing compoundinclude trimethylolpropane trimethacrylate, triallyl1,3,5-benzenetricarboxylate, triallyl trimellitate, tetraallylpyromellitate, pentaerythritol triacrylate, pentaerythritoltetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritolhexaacrylate, trimethylolpropane triacrylate, ditrimethylolpropanetetraacrylate, NK ESTER 1G, 2G, 3G, 4G, 9G, 14G, NPG, BPE-100, BPE-200,BPE-500, BPE-1400, A-200, A-400, A-600, TMPT and A-TMM-3 (trade names,produced by Shin-Nakamura Chemical Co., Ltd.), BANI-M, BANI-X (tradenames, produced by Maruzen Petrochemical Co., Ltd), etc. In view ofelongation and heat resistance of the obtained heat-cured film,trimethylolpropane trimethacrylate, triallyl1,3,5-benzenetricarboxylate, triallyl trimellitate, tetraallylpyromellitate, pentaerythritol triacrylate, pentaerythritoltetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritolhexaacrylate, trimethylolpropane triacrylate, ditrimethylolpropanetetraacrylate, BANI-M, and BANI-X are more preferred.

Specific preferably examples of the metal chelating agent include anacetylacetone aluminum(III) salt, an acetylacetone titanium(IV) salt, anacetylacetone chromium(III) salt, an acetylacetone magnesium(II) salt,an acetylacetone nickel(II) salt, a trifluoroacetylacetone aluminum(III)salt, a trifluoroacetylacetone titanium(IV) salt, atrifluoroacetylacetone chromium(III) salt, a trifluoroacetylacetonemagnesium(II) salt, a trifluoroacetylacetone nickel(II) salt, etc.

In the embodiment, the blending amount of crosslinking agent (C) in thephotosensitive resin composition is preferably from 0.1 to 40 parts bymass, more preferably from 1 to 30 parts by mass, per 100 parts by massof the resin constituting resin (A-1) or resin mixture (A-2). When theblending amount is 0.1 parts by mass or more, the thermophysicalproperties and mechanical strength of the heat-cured film are good, andwhen the blending amount is 40 parts by mass or less, the stability ofcomposition in the varnish state and the elongation of heat-cured filmare advantageous.

Among those crosslinking agents (C), in the case where the resin of thisembodiment has a carbonyl group, the polyhydric alcohol compound andpolyvalent amine compound can efficiently crosslink resins with eachother by means of a nucleophilic substitution reaction to the carbonylgroup.

Specific preferable polyhydric alcohol compound and polyvalent aminecompound include ethylene glycol, propylene glycol, 1,4-butanediol,1,6-hexanediol, 1,8-octanediol, 1,12-dodecanediol, glycerol,trimethylolethane, trimethylolpropane, DURANOL T6002, T6001, T5652,T5651, T5650J, T5650E, T4672, T4671, T4692, T4691, G3452 and G3450J(product names, produced by Asahi Kasei Chemicals Corp.),ethylenediamine, 1,3-propanediamine, 1,4-butanediamine,1,6-hexanediamine, 1,8-octanediamine, 1,12-dodecanediamine, etc.

[Thermal Acid Generator (D)]

From the standpoint that even when the curing temperature is lowered,good thermophysical properties and mechanical properties of the curedproduct are exhibited, it is preferable to further blend (D) a thermalacid generator in the photosensitive resin composition. Thermal acidgenerator (D) is a compound capable of generating an acid by heat andaccelerating the reaction of crosslinking agent (C). In addition, thetemperature at which thermal acid generator (D) generates an acid ispreferably from 150 to 250° C.

Specifically, thermal acid generator (D) includes, for example,carboxylic acid esters, such as allyl chloroacetate, n-butylchloroacetate, t-butyl chloroacetate, ethyl chloroacetate, methylchloroacetate, benzyl chloroacetate, isopropyl chloroacetate,2-methoxyethyl chloroacetate, methyl dichloroacetate, methyltrichloroacetate, ethyl trichloroacetate, 2-ethoxyethyltrichloroacetate, t-butyl cyanoacetate, t-butyl methacrylate, ethyltrifluoroacetate, methyl trifluoroacetate, phenyl trifluoroacetate,vinyl trifluoroacetate, isopropyl trifluoroacetate, allyltrifluoroacetate, ethyl benzoate, methyl benzoate, butyl benzoate,methyl 2-chlorobenzoate, ethyl 2-chlorobenzoate, ethyl 4-chlorobenzoate,ethyl 2,5-dichlorobenzoate, methyl 2,4-dichlorobenzoate, ethylp-fluorobenzoate, methyl p-fluorobenzoate, t-butylpentachlorophenylcarboxylate, methyl pentafluoropropionate, ethylpentafluoropropionate, t-butyl crotonate, etc.; cyclic carboxylic acidesters, such as phenolphthalein, thimolphthalein, etc.; sulfonic acidesters, such as ethyl methanesulfonate, methyl methanesulfonate,2-methoxyethyl methanesulfonate, 2-isopropoxyethyl methanesulfonate,methyl benzenesulfonate, phenyl p-toluenesulfonate, ethylp-toluenesulfonate, methyl p-toluenesulfonate, 2-phenylethylp-toluenesulfonate, n-propyl p-toluenesulfonate, n-butylp-toluenesulfonate, t-butyl p-toluenesulfonate, n-hexylp-toluenesulfonate, n-heptyl p-toluenesulfonate, n-octylp-toluenesulfonate, 2-methoxyethyl p-toluenesulfonate, propargylp-toluenesulfonate, 3-butynyl p-toluenesulfonate, ethyltrifluoromethanesulfonate, n-butyl trifluoromethanesulfonate, ethylperfluorobutanesulfonate, methyl perfluorobutanesulfonate, ethylperfluorooctanesulfonate, etc.; cyclic sulfonic acid esters, such as1,4-butanesultone, 2,4-butanesultone, 1,3-propanesultone, phenol red,bromocresol green, bromocresol purple, etc.; and 2-sulfobenzoicanhydride, p-toluenesulfonic anhydride, phthalic anhydride, etc.

Among these thermal acid generators (D), sulfonic acid esters, such asethyl methanesulfonate, methyl methanesulfonate, 2-methoxyethylmethanesulfonate, 2-isopropoxyethyl methanesulfonate, phenylp-toluenesulfonate, ethyl p-toluenesulfonate, methyl p-toluenesulfonate,2-methoxyethyl p-toluenesulfonate, ethyl trifluoromethanesulfonate,n-butyl trifluoromethanesulfonate, ethyl perfluorobutanesulfonate,methyl perfluorobutanesulfonate, ethyl perfluorooctanesulfonate,1,4-butanesultone, 2,4-butanesultone, etc.; 2-sulfobenzoic anhydride,and p-toluenesulfonic anhydride are preferred.

Furthermore, in view of adherence to a substrate, more preferablethermal acid generators (D) includes ethyl methanesulfonate, methylmethanesulfonate, 2-methoxyethyl methanesulfonate, ethylp-toluenesulfonate, methyl p-toluenesulfonate, 2-methoxyethylp-toluenesulfonate, ethyl trifluoromethanesulfonate, n-butyltrifluoromethanesulfonate, 1,4-butanesultone, 2,4-butanesultone,2-sulfobenzoic anhydride, p-toluenesulfonic anhydride, etc.

One of thermal acid generators (D) described above may be used alone, ortwo or more thereof may be used in combination.

The blending amount of thermal acid generator (D) in the photosensitiveresin composition is preferably from 0.1 to 30 parts by mass, morepreferably from 0.5 to 10 parts by mass, still more preferably from 1 to5 parts by mass, per 100 parts by mass of the resin constituting resin(A-1) or resin mixture (A-2). When the blending amount is 0.1 parts bymass or more, an effect of maintaining the pattern profile afterheat-curing is caused, and when the blending amount is 30 parts by massor less, an adverse effect on the lithography performance is not causedand the composition stability is advantageously good.

[Other Components]

The photosensitive resin composition may contain, if desired, a solvent,a dye, a surfactant, a silane coupling agent, a dissolution accelerator,a crosslinking accelerator, etc.

The solvent includes, for example, amides, sulfoxides, ureas, ketones,esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, etc.More specifically, the solvent that can be used includes, for example,N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide,dimethylsulfoxide, tetramethylurea, acetone, methyl ethyl ketone, methylisobutyl ketone, cyclopentanone, cyclohexanone, methyl acetate, ethylacetate, butyl acetate, diethyl oxalate, ethyl lactate, methyl lactate,butyl lactate, γ-butyrolactone, propylene glycol monomethyl etheracetate, propylene glycol monomethyl ether, benzyl alcohol, phenylglycol, tetrahydrofurfuryl alcohol, ethylene glycol dimethyl ether,diethylene glycol dimethyl ether, tetrahydrofuran, morpholine,dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene,o-dichlorobenzene, anisole, hexane, heptane, benzene, toluene, xylene,mesitylene, etc. In view of solubility of the resin, stability of theresin composition, and adhesiveness to a substrate,N-methyl-2-pyrrolidone, dimethylsulfoxide, tetramethylurea, butylacetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethylether acetate, propylene glycol monomethyl ether, benzyl alcohol, phenylglycol, and tetrahydrofurfuryl alcohol are preferred.

In the embodiment, the amount of the solvent used in the photosensitiveresin composition is preferably from 100 to 1,000 parts by mass, morepreferably from 120 to 700 parts by mass, still more preferably from 125to 500 parts by mass, per 100 parts by mass of phenolic resin (A-1).

The dye includes, for example, methyl violet, crystal violet, malachitegreen, etc. The blending amount of the dye in the photosensitive resincomposition is preferably from 0.1 to 30 parts by mass per 100 parts bymass of phenolic resin (A-1).

The surfactant includes a nonionic surfactant, for example, polyglycols,such as polypropylene glycol, polyoxyethylene lauryl ether, etc., andderivatives thereof; for example, a fluorine-containing surfactant, suchas FLUORAD (registered trademark and trade name, produced by Sumitomo 3MLimited), MEGAFACE (registered trademark and trade name, produced byDainippon Ink & Chemicals, Inc.), LUMIFLON (registered trademark andtrade name, produced by Asahi Glass Co., Ltd.), etc.; and, for example,an organic siloxane surfactant, such as KP 341 (trade name, produced byShin-Etsu Chemical Co., Ltd.), DBE (trade name, produced by ChissoCorporation), GLANOL (trade name, produced by Kyoeisha Chemical Co.,Ltd), etc.

The blending amount of the surfactant in the photosensitive resincomposition is preferably from 0.01 to 10 parts by mass per 100 parts bymass of the resin constituting resin (A-1) or resin mixture (A-2).

The silane coupling agent includes, although is not limited to, forexample, 3-mercaptopropyltrimethoxysilane (for example, trade name:KBM803 produced by Shin-Etsu Chemical Co., Ltd., trade name: Sila-Ace5810 produced by Chisso Corporation, etc.),3-mercaptopropyltriethoxysilane (trade name: SIM6475.0 produced by AZmaxCo.), 3-mercaptopropylmethyldimethoxysilane (for example, trade name:LS1375 produced by Shin-Etsu Chemical Co., Ltd., trade name: SIM6474.0produced by AZmax Co., etc.), mercaptomethyltrimethoxysilane (tradename: SIM6473.5C produced by AZmax Co.), mercaptomethyltrimethoxysilane(trade name: SIM6473.0 produced by AZmax Co.),3-mercaptopropyldiethoxymethoxysilane,3-mercaptopropylethoxydimethoxysilane, 3-mercaptopropyltripropoxysilane,3-mercaptopropyldiethoxypropoxysilane,3-mercaptopropylethoxydipropoxysilane,3-mercaptopropyldimethoxypropoxysilane,3-mercaptopropylmethoxydipropoxysilane, 2-mercaptoethyltrimethoxysilane,2-mercaptoethyldiethoxymethoxysilane,2-mercaptoethylethoxydimethoxysilane, 2-mercaptoethyltripropoxysilane,2-mercaptoethyltripropoxysilane, 2-mercaptoethylethoxydipropoxysilane,2-mercaptoethyldimethoxypropoxysilane,2-mercaptoethylmethoxydipropoxysilane, 4-mercaptobutyltrimethoxysilane,4-mercaptobutyltriethoxysilane, 4-mercaptobutyltripropoxysilane, etc.

The silane coupling agent also includes, although is not limited to, forexample, N-(3-triethoxysilylpropyl)urea (trade name: LS3610 produced byShin-Etsu Chemical Co., Ltd., trade name: SIU9055.0 produced by AZmaxCo.), N-(3-trimethoxysilylpropyl)urea (trade name: SIU9058.0 produced byAZmax Co.), N-(3-diethoxymethoxysilylpropyl)urea,N-(3-ethoxydimethoxysilylpropyl)urea, N-(3-tripropoxysilylpropyl)urea,N-(3-diethoxypropoxysilylpropyl)urea,N-(3-ethoxydipropoxysilylpropyl)urea,N-(3-dimethoxypropoxysilylpropyl)urea,N-(3-methoxydipropoxysilylpropyl)urea, N-(3-trimethoxysilylethyl)urea,N-(3-ethoxydimethoxysilylethyl)urea, N-(3-tripropoxysilylethyl)urea,N-(3-tripropoxysilylethyl)urea, N-(3-ethoxydipropoxysilylethyl)urea,N-(3-dimethoxypropoxysilylethyl)urea,N-(3-methoxydipropoxysilylethyl)urea, N-(3-trimethoxysilylbutyl)urea,N-(3-triethoxysilylbutyl)urea, N-(3-tripropoxysilylbutyl)urea,3-(m-aminophenoxy)propyltrimethoxysilane (trade name: SLA0598.0 producedby AZmax Co.), m-aminophenyltrimethoxysilane (trade name: SLA0599.0produced by AZmax Co.), p-aminophenyltrimethoxysilane (trade name:SLA0599.1 produced by AZmax Co.), aminophenyltrimethoxysilane (tradename: SLA0599.2 produced by AZmax Co.), 2-(trimethoxysilylethyl)pyridine(trade name: SIT8396.0 produced by AZmax Co.).

In addition, the silane coupling agent includes, although is not limitedto, for example, 2-(triethoxysilylethyl)pyridine,2-(dimethoxysilylmethylethyl)pyridine,2-(diethoxysilylmethylethyl)pyridine,(3-triethoxysilylpropyl)-t-butylcarbamate,(3-glycidoxypropyl)triethoxysilane, tetramethoxysilane,tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane,tetra-n-butoxysilane, tetra-i-butoxysilane, tetra-t-butoxysilane,tetrakis(methoxyethoxysilane), tetrakis(methoxy-n-propoxysilane),tetrakis(ethoxyethoxysilane), tetrakis(methoxyethoxyethoxysilane),bis(trimethoxysilyl)ethane, bis(trimethoxysilyl)hexane,bis(triethoxysilyl)methane, bis(triethoxysilyl)ethane,bis(triethoxysilyl)ethylene, bis(triethoxysilyl)octane,bis(triethoxysilyl)octadiene, bis[3-(triethoxysilyl)propyl]disulfide,bis[3-(triethoxysilyl)propyl]tetrasulfide, di-t-butoxydiacetoxysilane,di-i-butoxyaluminoxytriethoxysilane,bis(pentadionate)titanium-O,O′-bis(oxyethyl)-aminopropyltriethoxysilane,phenylsilanetriol, methylphenylsilanediol, ethylphenylsilanediol,n-propylphenylsilanediol, isopropylphenylsilanediol,n-butyldiphenylsilanediol, isobutylphenylsilanediol,tert-butylphenylsilanediol, diphenylsilanediol, dimethoxydiphenylsilane,diethoxydiphenylsilane, dimethoxydi-p-tolylsilane,ethylmethylphenylsilanol, n-propylmethylphenylsilanol,isopropylmethylphenylsilanol, n-butylmethylphenylsilanol,isobutylmethylphenylsilanol, tert-butylmethylphenylsilanol, ethyln-propylphenylsilanol, ethylisopropylphenylsilanol,n-butylethylphenylsilanol, isobutylethylphenylsilanol,tert-butylethylphenylsilanol, methyldiphenylsilanol,ethyldiphenylsilanol, n-propyldiphenylsilanol, isopropyldiphenylsilanol,n-butyldiphenylsilanol, isobutyldiphenylsilanol,tert-butyldiphenylsilanol, triphenylsilanol, etc.

Among the above-listed silane coupling agents, in view of storagestability, phenylsilanetriol, trimethoxyphenylsilane,trimethoxy(p-tolyl)silane, diphenylsilanediol, dimethoxydiphenylsilane,diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, triphenylsilanol, andsilane coupling agents represented by the following structures arepreferred.

The blending amount of the silane coupling agent in the photosensitiveresin composition is preferably from 0.01 to 20 parts by mass per 100parts by mass of resin (A-1) or resin mixture (A-2).

The dissolution accelerator includes, for example, a compound having ahydroxyl group or a carboxyl group. Examples of the compound having ahydroxyl group include a linear phenolic compound, such as ballastingagents used in naphthoquinonediazide compounds recited above,para-cumylphenol, bisphenols, resorcinols, MtrisPC, MtetraPC, etc.; anonlinear phenolic compound, such as TrisP-HAP, TrisP-PHBA, TrisP-PA(all produced by Honshu Chemical Industry Co. Ltd.), etc.; from 2 to 5phenolic substitution products of diphenylmethane, from 1 to 5 phenolicsubstitution products of 3,3-diphenylpropane, a compound obtained byreacting 2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane and5-norbornene-2,3-dicarboxylic anhydride in a molar ratio of 1:2, acompound obtained by reacting bis-(3-amino-4-hydroxyphenyl)sulfone and1,2-cyclohexyldicarboxylic anhydride in a molar ratio of 1:2,N-hydroxysuccinic acid imide, N-hydroxyphthalic acid imide, N-hydroxy5-norbornene-2,3-dicarboxylic acid imide, etc.

Examples of the compound having a carboxyl group include 3-phenyllacticacid, 4-hydroxyphenyllactic acid, 4-hydroxymandelic acid,3,4-dihydroxymandelic acid, 4-hydroxy-3-methoxymandelic acid,2-methoxy-2-(1-naphthyl)propionic acid, mandelic acid, atrolactic acid,α-methoxyphenylacetic acid, O-acetylmandelic acid, itaconic acid,benzoic acid, o-toluic acid, m-toluic acid, p-toluic acid,2,3-dimethylbenzoic acid, 2,4-dimethylbenzoic acid, 2,5-dimethylbenzoicacid, 2,6-dimethylbenzoic acid, 3,4-dimethylbenzoic acid,3,5-dimethylbenzoic acid, 2,4,5-trimethylbenzoic acid,2,4,6-trimethylbenzoic acid, 4-vinylbenzoic acid, cumic acid,isobutylbenzoic acid, 4-propylbenzoic acid, salicylic acid,3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 2-acetylbenzoic acid,4-acetylbenzoic acid, 3-fluorobenzoic acid, 4-fluorobenzoic acid,4-fluoro-2-methylbenzoic acid, 5-fluoro-2-methylbenzoic acid, p-anisicacid, 4-amylbenzoic acid, 4-butylbenzoic acid, 4-tert-butylbenzoic acid,3,5-di-tert-butylbenzoic acid, 4-trifluoromethylbenzoic acid,4-hydroxymethylbenzoic acid, phthalic acid, 4-methylphthaic acid,4-hydroxyphthalic acid, 4-trifluoromethylbenzoic acid, 4-methoxyphthalicacid, phthalamic acid, isophthalic acid, terephthalic acid,2,5-dimethylbenzoic acid, monomethyl terephthalate, trimesic acid,trimellitic acid, hemimellitic acid, pyromellitic acid,benzenepentacarboxylic acid, mellitic acid, etc.

The blending amount of the dissolution accelerator in the photosensitiveresin composition is preferably from 0.1 to 30 parts by mass per 100parts by mass of the resin constituting resin (A-1) or resin mixture(A-2).

The crosslinking accelerator is preferably a compound capable ofgenerating an acid by light or generating a base or a radical by heat orlight.

The compound capable of generating an acid by light includes, forexample, an onium salt, such as TPS-105 and 1000, DTS-105, NDS-105 and165 (trade names, produced by Midori Kagaku Co., Ltd.), DPI-DMAS,TTBPS-TF, TPS-TF, DTBPI-TF (trade names, produced by Toyo Gosei Co.,Ltd.), etc.; and an oxime sulfonate, such as NAI-100, 101, 105 and 106,PAI-101 (trade names, produced by Midori Kagaku Co., Ltd.), IRGACUREPAG-103, 108, 121 and 203, CGI-1380 and 725, NIT, 1907, PNBT (tradenames, produced by BASF Japan Inc.), etc.

The compound capable of generating a base by heat or light includes, forexample, an amine salt, such as U-CATSA-1, 102, 506, 603 and 810 (tradenames, produced by San-Apro Ltd.), CGI-1237, 1290 and 1293 (trade names,produced by BASF Japan Inc.), etc.; and a compound in which an aminogroup of 2,6-piperidine, butylamine, diethylamine, dibutylamine,N,N′-diethyl-1,6-diaminohexane, hexamethylenediamine, etc., is convertedto a urethane group or a urea group. The urethane group includes at-butoxycarbonylamino group, etc., and the urea group includes aphenylaminocarbonylamino group, etc.

The compound capable of generating a radical by heat or light includes,for example, an alkylphenone, such as IRGACURE 651, 184, 2959, 127, 907,369 and 379 (trade names, produced by BASF Japan Inc.), etc.; anacylphosphine oxide, such as IRGACURE 819 (trade name, produced by BASFJapan Inc.), etc.; a titanocene, such as IRGACURE 784 (trade name,produced by BASF Japan Inc.), etc.; and an oxime ester, such as IRGACUREOXE 01 and 02 (trade names, produced by BASF Japan Inc.), etc.

<Method for Forming Cured Relief Pattern>

In another embodiment, a method for producing a cured relief pattern byusing the above-described photosensitive resin composition is provided.The production method of a cured relief pattern comprises the followingsteps:

a step of forming (applying), on a substrate, a photosensitive resinlayer containing the photosensitive resin composition,

a step of exposing the photosensitive resin layer to light,

a step of developing the exposed photosensitive resin layer to form arelief pattern, and

a step of heat-treating the relief pattern to form a cured reliefpattern.

One example of the production method of a cured relief pattern isdescribed below.

First, the above-described photosensitive resin composition is appliedonto an appropriate support or substrate, for example, a silicon wafer,a ceramic, an aluminum substrate, etc. At the applying, in order toensure water-resistant adhesiveness between the pattern formed and thesupport, an adhesion aid, such as silane coupling agent may bepreviously applied on the support or substrate. Applying thephotosensitive resin composition is carried out by spin coating using aspinner, spray coating using a spray coater, dipping, printing, rollcoating, etc.

Next, the applied film of the photosensitive resin compositioncontaining phenolic resin (A-1) is dried by prebaking at 80 to 140° C.,and the photosensitive resin composition is then exposed to light. Asthe chemical ray for exposure, an X-ray, an electron beam, anultraviolet ray, visible light, etc., can be used, and a chemical rayhaving a wavelength of 200 to 500 nm is preferred. In view of resolutionand handling of a pattern, the light source wavelength is preferablyg-line, h-line or i-line of a mercury lamp, and one of these chemicalrays may be used alone, or two or more thereof may be mixed. As theexposure apparatus, a contact aligner, a mirror projection, and astepper are particularly preferred. After the exposure, the applied filmmay be again heated at 80 to 140° C., if desired.

Subsequently, development is carried out by a dipping method, a puddlingmethod, a spin spraying method, etc. The exposed area (in the case of apositive type) or unexposed area (in the case of a negative type) iseluted and removed from the applied photosensitive resin composition bydevelopment, whereby a relief pattern can be obtained.

The developer that can be used includes, for example, an aqueoussolution of inorganic alkalis, such as sodium hydroxide, sodiumcarbonate, sodium silicate, aqueous ammonia, etc., organic amines, suchas ethylamine, diethylamine, triethylamine, triethanolamine, etc., orquaternary ammonium salts, such as tetramethylammonium hydroxide,tetrabutylammonium hydroxide, etc. If necessary, a water-soluble organicsolvent, such as methanol, ethanol, etc., or a surfactant is added in anappropriate amount to the aqueous solution. Among these, an aqueoustetramethylammonium hydroxide solution is preferred. The concentrationof tetramethylammonium hydroxide is preferably from 0.5 to 10 mass %,more preferably from 1 to 5 mass %.

After the development, cleaning with a rinsing solution is carried outto remove the developer, whereby a pattern film can be obtained. As therinsing solution, for example, one of distilled water, methanol,ethanol, isopropanol, etc. may be used alone, or two or more thereof maybe used in combination.

Finally, the thus-obtained relief pattern is heated, whereby a curedrelief pattern can be obtained. The heating temperature is preferablyfrom 150 to 300° C., more preferably 250° C. or less.

In the usual method of forming a cured relief pattern by using apolyimide or polybenzoxazole precursor composition it is necessary toconvert the precursor to polyimide or polybenzoxazole by heating thecomposition at a temperature more than 300° C. to cause a dehydratingcyclization reaction. However, in the production method of a curedrelief pattern of the present invention, such heating is not necessary,so that the production method can be suitably used also for a thermallyweak semiconductor device, etc. In one example, the production method ofa cured relief pattern is suitably used for a semiconductor devicehaving an insulating layer consisting of a high-dielectric material orferroelectric material having a restriction on the processingtemperature, for example, an oxide of a metal having a high meltingpoint, such as titanium, tantalum, hafnium, etc. In the case where asemiconductor device is free from such a restriction in terms of heatresistance, also in the embodiment, a heat treatment at 300 to 400° C.may be of course carried out. Such a heat treatment can be carried outusing a hot plate, an oven, or a temperature-programmabletemperature-rising oven. As the atmosphere gas in the heating treatment,air may be used, or an inert gas, such as nitrogen, argon, etc., mayalso be used. In the case where the heat treatment must be carried outat a lower temperature, the composition may be heated under reducedpressure by using a vacuum pump, etc.

<Semiconductor Device>

In another embodiment, a semiconductor device having a cured reliefpattern produced by the above-described method using the above-describedphotosensitive resin composition is also provided. In this embodiment,the semiconductor device has a semiconductor element and a cured filmprovided on the top of the semiconductor element, wherein the cured filmis the cured relief pattern described above. In addition, the curedrelief pattern may be laminated to come into direct contact with thesemiconductor element or may be laminated with interposition of anotherlayer on the element. For example, the cured film includes a surfaceprotective film, an interlayer insulating film, an insulating film forrewiring, a protective film for a flip-chip device, and a protectivefilm of a semiconductor device having a bump structure. In theembodiment, the semiconductor device can be manufactured by combining aknown method for manufacturing a semiconductor device and theabove-described production method of a cured relief pattern of thepresent invention.

<Display Device>

In another embodiment, a display device having a cured relief patternproduced by the above-described method using the above-describedphotosensitive resin composition is also provided. In this embodiment,the display device has a display element and a cured film provided onthe top of the display element, wherein the cured film is the curedrelief pattern described above. In addition, the cured relief patternmay be laminated to come into direct contact with the display element ormay be laminated with interposition of another layer on the element. Forexample, the cured film includes a surface protective film, aninsulating film and a planarization film for a TFT liquid crystaldisplay element or a color filter element; a projection for an MVAliquid crystal display device; and a cathode partition wall for anorganic EL element. In the embodiment, similarly to the semiconductordevice described above, the display device can be manufactured bycombining a known method for manufacturing a display device and theabove-described production method of a cured relief pattern.

Examples of the application of the display device include a protectivefilm obtained by forming a cured film of the above-describedphotosensitive resin composition on a display device, an insulating filmor a planarization film for a TFT element, a color filter, etc., aprojection for an MVA liquid crystal display device, etc., and a cathodepartition wall for an organic EL element, etc. As for the use methodthereof, in accordance with the application of the semiconductor device,a patterned cured film of the photosensitive resin composition is formedby the above-described method on a substrate on which a display elementor a color filter has been formed.

In another embodiment of the present invention, an alkali-soluble resincomposition containing an alkali-soluble resin and a solvent isprovided. The alkali-soluble resin composition is characterized in thata cured film obtained by coating the resin composition and curing thecoated resin composition at 200° C. satisfies all of following a) to c):

a) the stress at a film thickness of 7 μm is from 5 to 18 MPa,

b) the maximum value of tensile elongation of the film having a filmthickness of 10 μm is from 20 to 100%, and

c) the glass transition temperature at a film thickness of 10 μm is from180 to 300° C.

In recent years, mainly for reasons of the material of constituentmember and the structural design, a demand for a material capable ofbeing heated and cured at a lower temperature, for example, at atemperature of 200° C. or less, is increasing.

Accordingly, in such a case, it is necessary that even when cured at200° C., the cured film consisting of the alkali-soluble resincomposition has sufficient properties as a surface protective film orinterlayer insulating film of a semiconductor. The present inventorshave found that when a cured film obtained by curing the alkali-solubleresin composition at 200° C. satisfies all of a) to c), the cured filmexhibits excellent performance as a protective film of a semiconductordevice.

In the case of satisfying a), i.e., in the case where the stress is from5 to 18 MPa, when an insulating film is formed on a silicon wafer,warpage of the silicon wafer is suppressed.

In the case of satisfying b), i.e., in the case where the maximum valueof tensile elongation is from 20 to 100%, when the cured film is appliedas a surface protective film or interlayer insulating film of asemiconductor device, cracking is less likely to occur upon impositionof a stress due to heat and the reliability of the semiconductor devicecan be increased.

In the case of satisfying c), i.e., in the case where the glasstransition temperature is from 180 to 300° C., a semiconductor having acured film consisting of the resin composition can be mounted on aprinted board without involving deformation of the cured relief patterndue to heat applied when mounting the semiconductor on the board.

The alkali-soluble resin is not limited but in view of heat resistance,is preferably a resin selected from a polyimide precursor, a polyimide,a polybenzoxazole precursor, and a phenolic resin.

Above all, a resin mixture of a resin containing a structure representedby formula (1) and resins containing structures represented by formulae(7) and (8) is more preferred.

The solvent is not particularly limited and includes those describedabove.

From the standpoint of forming a fine pattern, it is also preferred thatthe alkali-soluble resin composition containing an alkali-soluble resinand a solvent further contains a photoacid generator.

The photoacid generator includes those described above.

In addition, in order to more improve thermal properties and mechanicalproperties of the cured product, it is preferable to further blend acrosslinking agent in the alkali-soluble resin composition.

The crosslinking agent includes those described above.

Furthermore, as for the thermal acid generator and other components,those described above can be also added.

In another embodiment of the present invention, a cured product obtainedby coating a substrate with a photosensitive resin layer consisting of apositive-type photosensitive resin composition containing a phenolicresin, a photoacid generator and a solvent, and subjecting the layer toexposure, development and curing is provided. The cured product ischaracterized in that, in a cross-sectional profile consisting of aspace moiety of 5 to 100 μm and a land moiety of 1 to 10 mm, thecross-sectional angle defined by an interior angle relative to the basematerial surface when a tangential line is drawn at a height of half thecured film thickness is from 40 to 90°.

When the cross-sectional angle of the cured product is 40° or more, awiring layer below the cured film can be prevented from being naked, andwhen the cross-sectional angle is 90° or less, stress concentration onthe cured film can be avoided, and the damage to a structure with thecured film can be reduced. The cross-sectional angle of the curedproduct is preferably from 40 to 85°, more preferably from 45 to 80°.

The substrate includes a silicon wafer, etc.

The exposure, development and curing conditions are not limited as longas a cured film giving a cured product having a cross-sectional angle offrom 40 to 90° is obtained, but the exposure, development and curing canbe carried out, for example, under the conditions described in followingExamples.

EXAMPLES

The present invention is described in detail below by referring toSynthesis Examples, Examples and Comparative Examples, but the presentinvention is not limited to them.

In Examples, the measurement conditions are as follows.

<Weight Average Molecular Weight (Mw)>

The weight average molecular weight was calculated in terms of standardpolystyrene (organic solvent-based standard sample, STANDARD SM-105produced by Showa Denko K.K.) by GPC. The GPC apparatus used and themeasurement conditions are as follows:

Pump: JASCO PU-980

Detector: JASCO RI-930

Column oven: JASCO CO-965 40° C.

Column: Shodex KD-806M, two columns in series

Mobile phase: 0.01 mol/l, LiBr/N-methylpyrrolidone

Flow velocity: 1.0 ml/min.

<Evaluation of Alkali Solubility>

The resin was dissolved in γ-butyrolactone to give a solid contentconcentration of 37 mass %, and a silicon wafer was spin-coated with thesolution and then placed on a hot plate. The silicon wafer andspin-coated film were prebaked on the hot plate at 120° C. for 180seconds to form a coating film having a thickness of 10 μm. The filmthickness was measured by a film thickness measurement system (LAMBDAACE) manufactured by Dainippon Screen Mfg. Co., Ltd. Thereafter, thefilm was dipped in an aqueous TMAH solution (AZ300MIF produced by AZElectronic Materials) of 2.38 mass % at a liquid temperature of 23.0° C.and then again measured for the film thickness, and based on the valuesobtained the dissolution rate of the coated film was calculated. Thealkali solubility was judged as “good” when the dissolution rate was0.01 μm/sec or more, and judged as “bad” when it was less than 0.01μm/sec. [0209]′

<Residual Film Ratio During Curing and Evaluation of Cured ReliefPattern Profile>

A silicon wafer was spin-coated with a photosensitive resin compositionand placed on a hot plate, and the silicon wafer and spin-coated filmwere prebaked on the hot plate at 120° C. for 180 seconds to form acoating film having a thickness of 10 μm. This coating film was exposedto irradiation with i-line at an exposure dose of 500 mJ/cm² by using astepper NSR2005i8A (manufactured by Nikon Corp.) having an exposurewavelength of i-line (365 nm) through a reticle with a test pattern.After the exposure, with respect to Examples 12, 13, 33, 59, 68, 70, 71and 72, the film was reheated on the hot plate at 120° C. for 180seconds. The film was then developed with an aqueous 2.38%tetramethylammonium hydroxide solution AZ-300MIF (produced by AZElectronic Materials) at 23° C. for 100 seconds in a developing machine(D-SPIN), rinsed with pure water, and cured at 225° C. or 250° C. for 1hour under nitrogen atmosphere in a vertical curing furnace VF200B(manufactured by Koyo Thermo Systems Co., Ltd.) to obtain a cured reliefpattern. At this time, the film thickness was measured with acontact-type film thickness measuring apparatus P-15 (manufactured byKLA-Tencor Corporation) before and after the curing, and the residualfilm ratio during curing was calculated.

In addition, the cured relief pattern profile was judged as “good” whenthe relief pattern of a 20 μm square was not buried after curing and theshape was maintained, and the cured relief pattern profile was judged as“bad” when the shape was collapsed and the pattern was buried. However,with respect to Examples 13, 33, 59, 68, 70, 71 and 72, since thepattern is of a negative type, the profile was judged as “bad” when thepattern profile was collapsed.

<Measurement of Tensile Elongation>

The sample for elongation measurement was produced by the followingmethod. A 6-inch silicon wafer substrate having an aluminum depositionlayer on the outermost surface thereof was spin-coated with each of thephotosensitive resin compositions obtained in Examples and ComparativeExamples to have a film thickness of about 10 μm after curing, andprebaked on a hot plate at 120° C. for 180 seconds to form a coatingfilm. The film thickness was measured by a film thickness measurementsystem (LAMBDA ACE) manufactured by Dainippon Screen Mfg. Co., Ltd. Thiscoating film was heated at 200° C., 225° C. or 250° C. for 1 hour undernitrogen atmosphere to obtain a film having a thickness of 10 μm. Theobtained resin cured film was cut into a width of 3 mm by means of adicing saw and then separated from the wafer by a treatment with anaqueous dilute hydrochloric acid solution. In this way, 20 samples wereobtained. After leaving each sample to stand still for 24 hours or morein an atmosphere of a temperature of 23° C. and a relative humidity of50%, the elongation was measured by a tensile tester (TENSILON). Theelongation of the film cured at 225° C. or 250° C. shows the averagevalue of 20 samples, and the elongation of the film cured at 200° C.shows the maximum value. The measurement conditions of the tensiletester were as follows:

Temperature: 23° C.

Relative humidity: 50%

Initial sample length: 50 mm

Testing speed: 40 mm/min

Load cell rating: 2 kgf

<Measurement of Glass Transition Temperature>

Similarly to the sample produced above for the measurement of tensileelongation, a cured film piece having a thickness of about 10 μm and awidth of 3 mm was produced and measured for the glass transitiontemperature using a thermal mechanical analyzer (model name: TMA-50manufactured by Shimadzu Corporation). The measurement conditions wereas follows.

Sample length: 10 mm

Constant load: 200 g/mm²

Measurement temperature range: from 25 to 400° C.

Temperature rise rate: 10° C./min

Measurement atmosphere: nitrogen atmosphere

<Measurement of Residual Stress>

A 6-inch silicon wafer having a thickness of 625 μm±25 μm whose warpagewas previously measured was spin-coated with each of the photosensitiveresin compositions obtained in Examples and Comparative Examples to havea film thickness of about 10 μm after curing, and prebaked on a hotplate at 120° C. for 180 seconds to form a coating film. The filmthickness was measured by a film thickness measurement system (LAMBDAACE) manufactured by Dainippon Screen Mfg. Co., Ltd. The coating filmwas heated at 200° C. for 1 hour under nitrogen atmosphere to obtain afilm having a thickness of 10 μm, and after leaving the obtained waferwith a cured film to stand still in an atmosphere of a temperature of23° C. and humidity of 50% for 24 hours, the residual stress of thewafer was measured by a residual stress measuring apparatus (model name:FLX-2320 manufactured by Tencor Corporation).

<Measurement of Cross-Sectional Angle>

A silicon wafer was spin-coated with the photosensitive resincomposition and placed on a hot plate, and the silicon wafer andspin-coated film were prebaked on the hot plate at 120° C. for 180seconds to form a coating film having a thickness of 10 μm. This coatingfilm was exposed to irradiation with i-line at an exposure dose of 500mJ/cm² by using a stepper NSR2005i8A (manufactured by Nikon Corp.)having an exposure wavelength of i-line (365 nm) through a reticle witha test pattern. After the exposure, with respect to Examples 12, 13, 33,58, 67, 69, 70 and 71, the film was reheated on the hot plate at 120° C.for 180 seconds. The film was then developed with an aqueous 2.38%tetramethylammonium hydroxide solution AZ-300MIF (produced by AZElectronic Materials) at 23° C. for 100 seconds in a developing machine(D-SPIN), rinsed with pure water, and cured at 200° C. for 1 hour undernitrogen atmosphere in a vertical curing furnace VF200B (manufactured byKoyo Thermo Systems Co., Ltd.) to obtain a cured relief pattern.Thereafter, the cross-sectional profile consisting of a space moiety of50 μm and a land moiety of 5 mm was observed using SEM (model name:S-4800 manufactured by Hitachi High-Technologies Corporation), and thecross-sectional angle defined by an interior angle relative to the basematerial surface when a tangential line is drawn at a height of half thecured film thickness was measured.

<¹H NMR Measurement Conditions>

Measuring apparatus: Model JNM-GSX 400 manufactured by JEOL Ltd.

Measurement temperature: 23° C.

Measurement solvent: deuterated dimethylsulfoxide solvent (DMSO-d₆)

The structures of photoacid generator (B), crosslinking agent (C) andthermal acid generator (D) used in Examples and Comparative Examples areas follows.

(B-1)

A photoacid generator shown by the following formula:

{wherein out of Q, 83% is a structure represented by the followingformula and the remaining is a hydrogen atom}:

(B-2)

IRGACURE PAG121 (trade name, produced by BASF Japan Inc.)

(B-3)

A photoacid generator shown by the following formula:

(C-1)

(NIKALAC MX-270, trade name, produced by Sanwa Chemical Co., Ltd.)

(C-2)

A crosslinking agent shown by the following formula:

triglycidyl isocyanurate

(C-3)

A crosslinking agent shown by the following formula:

{wherein n₈ is an integer of 1 to 3}ETERNACOLL OXBP (trade name, produced by Ube Industries, Ltd.)

(C-4)

A crosslinking agent shown by the following formula:

DURANATE TPA-B80E (trade name, produced by Asahi Kasei ChemicalsCorporation)

(C-5)

A crosslinking agent shown by the following formula:

p-xylylene glycol

(C-6):

DURANOL T5652 (product name, produced by Asahi Kasei Chemicals Corp.)

(C-7)

A crosslinking agent shown by the following formula:

2,6-Bis(hydroxymethyl)-p-cresol

(D-1)

A thermal acid generator shown by the following formula:

2-Methoxyethyl p-toluenesulfonateEP-4080G: Novolak resin, produced by Asahi Organic Chemicals IndustryCo., Ltd., weight average molecular weight=10,600MEH-7851-4H: Phenol-biphenyldiyl resin, produced by Meiwa PlasticIndustries, Ltd., weight average molecular weight=10,000, a structurerepresented by following formula (24)MEH-7851-SS: Phenol-biphenyldiyl resin, produced by Meiwa PlasticIndustries, Ltd., weight average molecular weight=1,600, a structurerepresented by following formula (24)

Synthesis Example 1 Synthesis of Resin P1-1

In a 0.5 liter-volume separable flask with a Dean-Stark device, 76.4 g(0.36 mol) of propyl gallate, 67.9 g (0.28 mol) of4,4′-bis(methoxymethyl)biphenyl, 2.2 g (0.014 mol) of diethylsulfuricacid, and 100 g of diglyme (hereinafter, sometimes referred to as“DMDG”) were mixed and stirred at 70° C. to dissolve solids.

The mixed solution was heated to 140° C. in an oil bath, and generationof methanol was confirmed by the reaction solution. In this state, thereaction solution was stirred at 140° C. for 5 hours.

Thereafter, the reaction vessel was cooled in the atmosphere, and 150 gof tetrahydrofuran was separately added thereto and stirred. Theresulting diluted reaction solution was added dropwise to 5 L of waterwith high-speed stirring to disperse and precipitate a resin, and theresin was recovered, appropriately washed with water, dewatered and thenvacuum-dried to obtain Resin (P1-1) at a yield of 76%. The weightaverage molecular weight by GPC of Resin (P1-1) thus synthesized was10,900 in terms of polystyrene. FIG. 1 shows the ¹H NMR spectrumobtained by dissolving P1-1 in a deuterated dimethylsulfoxide solventand measuring the solution by Model JNM-GSX 400 manufactured by JEOLLtd.

Synthesis Example 2 Synthesis of Resin P1-2

Synthesis was carried out in the same manner as in Synthesis Example 1by using 70.6 g (0.42 mol) of methyl 3,5-dihydroxybenzoate in place ofpropyl gallate of Synthesis Example 1, whereby Resin (P1-2) was obtainedat a yield of 78%. The weight average molecular weight by GPC of Resin(P1-2) synthesized was 14,600 in terms of polystyrene. FIG. 2 shows the¹H NMR spectrum obtained by measuring P1-2 in the same manner as inSynthesis Example 1

Synthesis Example 3 Synthesis of Resin P1-3

Synthesis was carried out in the same manner as in Synthesis Example 1by using 64.3 g (0.42 mol) of 2,4-dihydroxybenzamide in place of propylgallate of Synthesis Example 1, whereby Resin (P1-3) was obtained at ayield of 82%. The weight average molecular weight by GPC of Resin (P1-3)synthesized was 19,200 in terms of polystyrene.

Synthesis Example 4 Synthesis of Resin P1-4

Synthesis was carried out in the same manner as in Synthesis Example 1by using 71.0 g (0.47 mol) of 2,4-dihydroxyacetophenone in place ofpropyl gallate of Synthesis Example 1, whereby Resin (P1-4) was obtainedat a yield of 73%. The weight average molecular weight by GPC of Resin(P1-4) synthesized was 11,800 in terms of polystyrene.

Synthesis Example 5 Synthesis of Imidophenol Compound I-1

In 0.5 liter-volume separable flask, 54.6 g (0.5 mol) of 2-aminophenol,120 g of γ-butyrolactone (GBL), and 39.6 g (0.5 mol) of pyridine wereput, and 89.1 g (0.5 mol) of methyl-5-norbornene-2,3-dicarboxylicanhydride was charged thereinto at room temperature. After reaction withstirring overnight at room temperature, the reaction was confirmed bylow molecular GPC, as a result, raw materials were not detected at alland the product was detected as a single peak with a purity of 99%. Thisreaction solution was directly added dropwise with stirring to 2 literof ion-exchanged water to precipitate the product. The product wasseparated by filtration and then vacuum-dried to obtain ImidophenolCompound (I-1) having the following structure at a yield of 85%.

Synthesis of Resin P1-5

Synthesis was carried out in the same manner as in Synthesis Example 1by using 85.0 g (0.44 mol) of Compound (I-1) in place of propyl gallateof Synthesis Example 1, whereby Resin (P1-5) was obtained at a yield of58%. The weight average molecular weight by GPC of Resin (P1-5)synthesized was 3,900 in terms of polystyrene.

Synthesis Example 6 Synthesis of Resin P1-6

Synthesis was carried out in the same manner as in Synthesis Example 1by using 51.6 g (0.37 mol) of salicylic acid in place of propyl gallateof Synthesis Example 1, whereby Resin (P1-6) was obtained at a yield of71%. The weight average molecular weight by GPC of Resin (P1-6)synthesized was 18,200 in terms of polystyrene.

Synthesis Example 7 Synthesis of Resin P1-7

Synthesis was carried out in the same manner as in Synthesis Example 1by using 60.4 g (0.39 mol) of 2,4-dihydroxybenzoic acid in place ofpropyl gallate of Synthesis Example 1, whereby Resin (P1-7) was obtainedat a yield of 66%. The weight average molecular weight by GPC of Resin(P1-7) synthesized was 13,500 in terms of polystyrene.

Synthesis Example 8 Synthesis of Resin P1-8

Synthesis was carried out in the same manner as in Synthesis Example 1by using 60.6 g (0.44 mol) of 3-nitrophenol in place of propyl gallateof Synthesis Example 1, whereby Resin (P1-8) was obtained at a yield of70%. The weight average molecular weight by GPC of Resin (P1-8)synthesized was 11,500 in terms of polystyrene.

Synthesis Example 9 Synthesis of Resin P1-9

Synthesis was carried out in the same manner as in Synthesis Example 1by using 41.4 g (0.3 mol) of 1,4-bis(methoxymethyl)benzene in place of4,4′-bis(methoxymethyl)biphenyl of Synthesis Example 1, whereby Resin(P1-9) was obtained at a yield of 72%. The weight average molecularweight by GPC of Resin (P1-9) synthesized was 12,600 in terms ofpolystyrene.

Synthesis Example 10 Synthesis of Resin P1-10

Synthesis was carried out in the same manner as in Synthesis Example 1by using 50.5 g (0.3 mol) of 2,6-bis(hydroxymethyl)-p-cresol in place of4,4′-bis(methoxymethyl)biphenyl of Synthesis Example 1, whereby Resin(P1-10) was obtained at a yield of 74%. The weight average molecularweight by GPC of Resin (P1-10) synthesized was 13,400 in terms ofpolystyrene.

Synthesis Example 11 Synthesis of Resin P1-11

In a 0.5 liter-volume separable flask, 50 g of Resin P1-1 obtained inSynthesis Example 1 and 70 g of GBL were mixed and stirred to dissolvesolids. Thereafter, 26.2 g (0.12 mol) of di-tert-butyl dicarbonate wasadded dropwise together with 25 g of GBL. Furthermore, 4.7 g (0.06 mol)of pyridine was added dropwise together with 10 g of GBL, and thereaction was allowed to proceed at room temperature for 5 hours.

Thereafter, 100 g of tetrahydrofuran was separately added thereto andstirred, and the resulting diluted reaction solution was added dropwiseto 3 L of water with high-speed stirring to disperse and precipitate aresin. The resin was recovered, appropriately washed with water,dewatered and then vacuum-dried to obtain target Resin (P1-11) where 30%of all hydroxyl groups are protected by a tert-butoxycarbonyl group.

<Evaluation of Alkali Solubility>

Using Resins P1-1 to P1-10 obtained in Synthesis Examples 1 to 10, ResinP1-12 (EP-4080G, a novolak resin obtained by condensing a mixture ofm-cresol: p-cresol=60:40 with formaldehyde, produced by Asahi OrganicChemicals Industry Co., Ltd., weight average molecular weight=10,600),Resin P1-13 (MEH-7851-4H, a resin mainly containing aphenol-biphenyldiyl resin obtained by condensing phenol and4,4′-bis(methoxymethyl)biphenol, produced by Meiwa Plastic Industries,Ltd., weight average molecular weight=10,000) and Resin P1-14(MEH-7851-SS, a resin mainly containing a phenol-biphenyldiyl resinobtained by condensing phenol and 4,4′-bis(methoxymethyl)biphenyl,produced by Meiwa Plastic Industries, Ltd., weight average molecularweight=1,600), the alkali solubility was evaluated by theabove-described method. The results are shown in Table 1 below.

TABLE 1 Polymer P1-1 P1-2 P1-3 P1-4 P1-5 P1-6 P1-7 P1-8 P1-9 P1-10 P1-12P1-13 P1-14 Alkali dissolution 5.3 4.9 4.4 3.9 2.8 11.9 6.9 2.1 5.8 6.55.0 0.0 5.9 rate [*10⁻² um/sec] Evaluation of alkali good good good goodgood good good good good good good bad good solubility

Preparation and Evaluation of Positive-Type Photosensitive ResinComposition Example 1

100 Parts by mass of Resin (P1-1) obtained in Synthesis Example 1 and 12parts by mass of Photoacid Generator (B-1) were dissolved in 114 partsby mass of GBL, and the solution was filtered through a 0.1 μm filter toprepare a positive-type photosensitive resin composition. The resincomposition was evaluated for the cured relief pattern profile andtensile elongation. The evaluation results are shown in Table 2.

Example 2

Preparation and evaluation were carried out in the same manner as inExample 1, except that 20 parts by mass of Crosslinking Agent (C-1) wasfurther added in Example 1. The evaluation results are shown in Table 2.

Examples 3 to 11

Preparation and evaluation were carried out in the same manner as inExample 2, except that Resin P1-1 was replaced by Resins P1-2 to P1-10as shown in Table 3 in Example 2. The evaluation results are shown inTable 2.

Example 12

100 Parts by mass of Resin (P1-11) and 5 parts by mass of PhotoacidGenerator (B-2) were dissolved in 114 parts by mass of GBL, and thesolution was filtered through a 0.1 μm filter to prepare a positive-typephotosensitive resin composition. The resin composition was evaluatedfor the cured relief pattern profile and tensile elongation. Theevaluation results are shown in Table 2.

Example 13

100 Parts by mass of Resin (P1-1), 5 parts by mass of PhotoacidGenerator (B-2) and 20 parts by mass of Crosslinking Agent (C-1) weredissolved in 114 parts by mass of GBL, and the solution was filteredthrough a 0.1 filter to prepare a negative-type photosensitive resincomposition and evaluated for the cured relief pattern profile andtensile elongation. The evaluation results are shown in Table 2.

Example 14

Preparation and evaluation were carried out in the same manner as inExample 2, except that the amount added of Photoacid Generator-B-1 waschanged to 20 parts by mass in Example 2. The evaluation results areshown in Table 2.

Example 15

Preparation and evaluation were carried out in the same manner as inExample 2, except that the amount added of Crosslinking Agent C-1 waschanged to 40 parts by mass in Example 2. The evaluation results areshown in Table 2

Example 16

Preparation and evaluation were carried out in the same manner as inExample 2, except that 10 parts by mass of Crosslinking Agent C-2 wasadded in place of Crosslinking Agent C-1 in Example 2. The evaluationresults are shown in Table 2.

Example 17

Preparation and evaluation were carried out in the same manner as inExample 2, except that 20 parts by mass of Crosslinking Agent C-3 wasadded in place of Crosslinking Agent C-1 in Example 2. The evaluationresults are shown in Table 2.

Example 18

Preparation and evaluation were carried out in the same manner as inExample 2, except that 10 parts by mass of Crosslinking Agent C-4 wasadded in place of Crosslinking Agent C-1 in Example 2. The evaluationresults are shown in Table 2.

Example 19

Preparation and evaluation were carried out in the same manner as inExample 2, except that 10 parts by mass of Crosslinking Agent C-5 wasadded in place of Crosslinking Agent C-1 in Example 2. The evaluationresults are shown in Table 2.

Example 20

Preparation and evaluation were carried out in the same manner as inExample 2, except that 5 parts by mass of Crosslinking Agent C-6 wasadded in place of Crosslinking Agent C-1 in Example 2. The evaluationresults are shown in Table 2.

Comparative Example 1

Preparation and evaluation were carried out in the same manner as inExample 1, except that Resin P1-1 was replaced by Resin (P1-12) inExample 1. The evaluation results are shown in Table 2.

Comparative Example 2

Preparation and evaluation were carried out in the same manner as inExample 1, except that Resin P1-1 was replaced by Resin (P1-13) inExample 1. With respect to the cured relief pattern profile, a reliefpattern could not be formed due to insufficient alkali solubility,failing in evaluation. The evaluation results are shown in Table 2.

Comparative Example 3

Preparation and evaluation were carried out in the same manner as inExample 1, except that Resin P1-1 was replaced by Resin (P1-14) inExample 1. With respect to the cured relief pattern profile, the patternwas buried, and the evaluation was “bad”. The evaluation results areshown in Table 2.

Comparative Example 4

Preparation and evaluation were carried out in the same manner as inExample 2, except that Resin P1-1 was replaced by Resin (P1-14) inExample 2. With respect to the cured relief pattern profile, the patternwas buried, and the evaluation was “bad”. The evaluation results areshown in Table 2.

TABLE 2 Example 1 2 3 4 5 6 7 8 9 10 11 12 Polymer P1-1 P1-1 P1-2 P1-3P1-4 P1-5 P1-6 P1-7 P1-8 P1-9 P1-10 P1-11 Photoacid Generator B-1 12 1212 12 12 12 12 12 12 12 12 Photoacid Generator B-2 5 Crosslinking AgentC-1 20 20 20 20 20 20 20 20 20 20 Crosslinking Agent C-2 CrosslinkingAgent C-3 Crosslinking Agent C-4 Crosslinking Agent C-5 CrosslinkingAgent C-6 Cured relief pattern good good good good good good good goodgood good good good profile Elongation [%] 15 45 18 15 36 11 21 24 15 1915 17 Curing temperature [° C.] 250 250 250 250 250 250 250 250 250 250250 250 Example Comparative Example 13 14 15 16 17 18 19 20 1 2 3 4Polymer P1-1 P1-1 P1-1 P1-1 P1-1 P1-1 P1-1 P1-1 P1-12 P1-13 P1-14 P1-14Photoacid Generator B-1 20 12 12 12 12 12 12 12 12 12 12 PhotoacidGenerator B-2 5 Crosslinking Agent C-1 20 20 40 20 Crosslinking AgentC-2 10 Crosslinking Agent C-3 20 Crosslinking Agent C-4 10 CrosslinkingAgent C-5 10 Crosslinking Agent C-6 5 Cured relief pattern good goodgood good good good good good bad — bad bad profile Elongation [%] 21 4127 30 29 16 32 42 3 5 3 30 Curing temperature [° C.] 250 250 250 250 250250 250 250 250 250 250 250

Results shown in Table 2 reveal that the photosensitive resincomposition of the present invention has sufficient alkali solubility,is excellent in tensile elongation of the cured film, and gives a resinfilm ensuring a good cured relief pattern profile.

Synthesis Example 12 Synthesis of Resin P2-1

A 1.0 L-volume separable flask with a Dean-Stark device was purged withnitrogen and thereafter, in the separable flask, 91.8 g (0.833 mol) ofresorcin, 109.0 g (0.45 mol) of 4,4′-bis(methoxymethyl)biphenyl (BMMB),3.81 g (0.02 mol) of p-toluenesulfonic acid, and 116 g of propyleneglycol monomethyl ether (PGME) were mixed and stirred at 50° C. todissolve solids.

The mixed solution dissolved was heated to 120° C. in an oil bath, andgeneration of methanol was confirmed by the reaction solution. In thisstate, the reaction solution was stirred at 120° C. for 3 hours.

Subsequently, 8.3 g (0.050 mol) of 2,6-bis(hydroxymethyl)-p-cresol and83 g of PGME were mixed and stirred in a separate vessel, and theresulting uniformly dissolved solution was added dropwise over 1 hour tothe separable flask by using a dropping funnel. After the dropwiseaddition, the system was further stirred for 2 hours.

After the completion of reaction, the reaction vessel was cooled in theatmosphere, and 50 g of PGME was separately added thereto and stirred.The resulting diluted reaction solution was added dropwise to 8 L ofwater with high-speed stirring to disperse and precipitate a resin, andthe resin was recovered, appropriately washed with water, dewatered andthen vacuum-dried to obtain Resin (P2-1) at a yield of 78%. The weightaverage molecular weight by GPC of Resin (P2-1) thus synthesized was6,600 in terms of polystyrene. FIG. 3 shows the NMR spectrum obtained bydissolving P2-1 in a deuterated dimethylsulfoxide solvent and measuringthe solution by Model JNM-GSX 400 manufactured by JEOL Ltd.

Synthesis Example 13 Synthesis of Resin P2-2

A 1.0 L-volume separable flask with a Dean-Stark device was purged withnitrogen and thereafter, in the separable flask, 85.6 g (0.778 mol) ofresorcin, 96.9 g (0.40 mol) of BMMB, 3.81 g (0.02 mol) ofp-toluenesulfonic acid, and 116 g of propylene glycol monomethyl ether(PGME) were mixed and stirred at 50° C. to dissolve solids.

The mixed solution dissolved was heated to 120° C. in an oil bath, andgeneration of methanol was confirmed by the reaction solution. In thisstate, the reaction solution was stirred at 120° C. for 3 hours.

Subsequently, 16.2 g (0.100 mol) of 2,6-bis(hydroxymethyl)-p-cresol and162 g of PGME were mixed and stirred in a separate vessel, and theresulting uniformly dissolved solution was added dropwise over 1 hour tothe separable flask by using a dropping funnel. After the dropwiseaddition, the system was further stirred for 2 hours. After thecompletion of reaction, the same processing as in Synthesis Example 12was carried out to obtain Resin (P2-2) at a yield of 77%. The weightaverage molecular weight by GPC of Resin (P2-2) synthesized was 9,000 interms of polystyrene. FIG. 4 shows the NMR spectrum obtained bymeasuring P2-2 in the same manner as in Synthesis Example 12.

Synthesis Example 14 Synthesis of Resin P2-3

A 1.0 L-volume separable flask with a Dean-Stark device was purged withnitrogen and thereafter, in the separable flask, 81.3 g (0.738 mol) ofresorcin, 84.8 g (0.35 mol) of BMMB, 3.81 g (0.02 mol) ofp-toluenesulfonic acid, and 116 g of propylene glycol monomethyl ether(PGME) were mixed and stirred at 50° C. to dissolve solids.

The mixed solution dissolved was heated to 120° C. in an oil bath, andgeneration of methanol was confirmed by the reaction solution. In thisstate, the reaction solution was stirred at 120° C. for 3 hours.

Subsequently, 24.9 g (0.150 mol) of 2,6-bis(hydroxymethyl)-p-cresol and249 g of PGME were mixed and stirred in a separate vessel, and theresulting uniformly dissolved solution was added dropwise over 1 hour tothe separable flask by using a dropping funnel. After the dropwiseaddition, the system was further stirred for 2 hours.

After the completion of reaction, the same processing as in SynthesisExample 12 was carried out to obtain Resin (P2-3) at a yield of 77%. Theweight average molecular weight by GPC of Resin (P2-3) synthesized was9,900 in terms of polystyrene. FIG. 5 shows the NMR spectrum obtained bymeasuring P2-3 in the same manner as in Synthesis Example 12.

Synthesis Example 15 Synthesis of Resin P2-4

A 1.0 L-volume separable flask with a Dean-Stark device was purged withnitrogen and thereafter, in the separable flask, 78.0 g (0.708 mol) ofresorcin, 72.7 g (0.30 mol) of BMMB, 3.81 g (0.02 mol) ofp-toluenesulfonic acid, and 116 g of propylene glycol monomethyl ether(PGME) were mixed and stirred at 50° C. to dissolve solids.

The mixed solution dissolved was heated to 120° C. in an oil bath, andgeneration of methanol was confirmed by the reaction solution. In thisstate, the reaction solution was stirred at 120° C. for 3 hours.

Subsequently, 33.2 g (0.200 mol) of 2,6-bis(hydroxymethyl)-p-cresol and332 g of PGME were mixed and stirred in a separate vessel, and theresulting uniformly dissolved solution was added dropwise over 1 hour tothe separable flask by using a dropping funnel. After the dropwiseaddition, the system was further stirred for 2 hours.

After the completion of reaction, the same processing as in SynthesisExample 12 was carried out to obtain Resin (P2-4) at a yield of 79%. Theweight average molecular weight by GPC of Resin (P2-4) synthesized was11,500 in terms of polystyrene. FIG. 6 shows the NMR spectrum obtainedby measuring P2-4 in the same manner as in Synthesis Example 12.

Synthesis Example 16 Synthesis of Resin P2-5

A 1.0 L-volume separable flask with a Dean-Stark device was purged withnitrogen and thereafter, in the separable flask, 73.7 g (0.667 mol) ofresorcin, 48.5 g (0.20 mol) of BMMB, 3.81 g (0.02 mol) ofp-toluenesulfonic acid, and 116 g of propylene glycol monomethyl ether(PGME) were mixed and stirred at 50° C. to dissolve solids.

The mixed solution dissolved was heated to 120° C. in an oil bath, andgeneration of methanol was confirmed by the reaction solution. In thisstate, the reaction solution was stirred at 120° C. for 3 hours.

Subsequently, 49.9 g (0.300 mol) of 2,6-bis(hydroxymethyl)-p-cresol and499 g of PGME were mixed and stirred in a separate vessel, and theresulting uniformly dissolved solution was added dropwise over 1 hour tothe separable flask by using a dropping funnel. After the dropwiseaddition, the system was further stirred for 2 hours. After thecompletion of reaction, the same processing as in Synthesis Example 12was carried out to obtain Resin (P2-5) at a yield of 81%. The weightaverage molecular weight by GPC of Resin (P2-5) synthesized was 18,500in terms of polystyrene.

Synthesis Example 17 Synthesis of Resin P2-6

A 1.0 L-volume separable flask with a Dean-Stark device was purged withnitrogen and thereafter, in the separable flask, 88.3 g (0.700 mol) ofpyrogallol, 96.9 g (0.40 mol) of BMMB, 3.81 g (0.02 mol) ofp-toluenesulfonic acid, and 130 g of propylene glycol monomethyl ether(PGME) were mixed and stirred at 50° C. to dissolve solids.

The mixed solution dissolved was heated to 115° C. in an oil bath, andgeneration of methanol was confirmed by the reaction solution. In thisstate, the reaction solution was stirred at 120° C. for 3 hours.

Subsequently, 16.6 g (0.100 mol) of 2,6-bis(hydroxymethyl)-p-cresol and166 g of PGME were mixed and stirred in a separate vessel, and theresulting uniformly dissolved solution was added dropwise over 1 hour tothe separable flask by using a dropping funnel. After the dropwiseaddition, the system was further stirred for 2 hours. After thecompletion of reaction, the same processing as in Synthesis Example 12was carried out to obtain Resin (P2-6) at a yield of 81%. The weightaverage molecular weight by GPC of Resin (P2-6) synthesized was 11,200in terms of polystyrene. FIG. 7 shows the NMR spectrum obtained bymeasuring P2-6 in the same manner as in Synthesis Example 12.

Synthesis Example 18 Synthesis of Resin P2-7

A 1.0 L-volume separable flask with a Dean-Stark device was purged withnitrogen and thereafter, in the separable flask, 119.7 g (0.738 mol) ofphloroglucinol dihydrate, 109.0 g (0.45 mol) of BMMB, 3.81 g (0.02 mol)of p-toluenesulfonic acid, and 130 g of propylene glycol monomethylether (PGME) were mixed and stirred at 50° C. to dissolve solids.

The mixed solution dissolved was heated to 120° C. in an oil bath, andgeneration of methanol was confirmed by the reaction solution. In thisstate, the reaction solution was stirred at 120° C. for 3 hours.

Subsequently, 8.3 g (0.100 mol) of 2,6-bis(hydroxymethyl)-p-cresol and83 g of PGME were mixed and stirred in a separate vessel, and theresulting uniformly dissolved solution was added dropwise over 1 hour tothe separable flask by using a dropping funnel. After the dropwiseaddition, the system was further stirred for 2 hours. After thecompletion of reaction, the same processing as in Synthesis Example 12was carried out to obtain Resin (P2-7) at a yield of 84%. The weightaverage molecular weight by GPC of Resin (P2-7) synthesized was 21,000in terms of polystyrene. FIG. 8 shows the NMR spectrum obtained bymeasuring P2-7 in the same manner as in Synthesis Example 12.

Synthesis Example 19 Synthesis of Resin P2-8

Synthesis was carried out in the same manner as in Synthesis Example 15by using 39.6 g (0.200 mol) of 2,6-bis(hydroxymethyl)-4-ethoxyphenol inplace of 33.2 g (0.200 mol) of 2,6-bis(hydroxymethyl)-p-cresol ofSynthesis Example 15, whereby Resin (P2-8) was obtained at a yield of82%. The weight average molecular weight by GPC of Resin (P2-8)synthesized was 10,800 in terms of polystyrene.

Synthesis Example 20 Synthesis of Resin P2-9

Synthesis was carried out in the same manner as in Synthesis Example 15by using 47.7 g (0.200 mol) of 2,6-bis(hydroxymethyl)-4-t-butylphenol inplace of 33.2 g (0.200 mol) of 2,6-bis(hydroxymethyl)-p-cresol ofSynthesis Example 15, whereby Resin (P2-9) was obtained at a yield of80%. The weight average molecular weight by GPC of Resin (P2-9)synthesized was 10,200 in terms of polystyrene.

Synthesis Example 21 Synthesis of Resin P2-10

A 1.0 L-volume separable flask with a Dean-Stark device was purged withnitrogen and thereafter, in the separable flask, 91.8 g (0.833 mol) ofresorcin, 82.1 g (0.18 mol) of TML-BPAF-MF (product name of HonshuChemical Industry Co., Ltd.), 3.81 g (0.02 mol) of p-toluenesulfonicacid, and 116 g of propylene glycol monomethyl ether (PGME) were mixedand stirred at 50° C. to dissolve solids.

The mixed solution dissolved was heated to 120° C. in an oil bath, andgeneration of methanol was confirmed by the reaction solution. In thisstate, the reaction solution was stirred at 120° C. for 3 hours.

Subsequently, 41.5 g (0.25 mol) of 2,6-bis(hydroxymethyl)-p-cresol and83 g of PGME were mixed and stirred in a separate vessel, and theresulting uniformly dissolved solution was added dropwise over 1 hour tothe separable flask by using a dropping funnel. After the dropwiseaddition, the system was further stirred for 2 hours. After thecompletion of reaction, the reaction vessel was cooled in theatmosphere, and 50 g of PGME was separately added thereto and stirred.The resulting diluted reaction solution was added dropwise to 8 L ofwater with high-speed stirring to disperse and precipitate a resin, andthe resin was recovered, appropriately washed with water, dewatered andthen vacuum-dried to obtain Resin (P2-10) at a yield of 75%. The weightaverage molecular weight by GPC of Resin (P2-10) thus synthesized was8,600 in terms of polystyrene.

The structure of TML-BPAF-MF is shown below.

Synthesis Example 22 Synthesis of Resin P2-11

Synthesis was carried out in the same manner as in Synthesis Example 12by using 72.8 g (0.18 mol) of TMOM-BPA (product name of Honshu ChemicalIndustry Co., Ltd.) in place of 82.1 g (0.18 mol) of TML-BPAF-MF(product name of Honshu Chemical Industry Co., Ltd.) of SynthesisExample 21, whereby Resin (P2-11) was obtained at a yield of 73%. Theweight average molecular weight by GPC of Resin (P2-11) synthesized was7,600 in terms of polystyrene.

The structure of TMOM-BPA is shown below.

<Evaluation Results of Alkali Solubility>

Using Resins P2-1 to P2-11 obtained in Synthesis Examples 12 to 22,Resin P2-12 (EP-4080G, a novolak resin, produced by Asahi OrganicChemicals Industry Co., Ltd., weight average molecular weight=10,600),Resin P2-13 (MEH-7851-4H, a phenol-biphenyldiyl resin, produced by MeiwaPlastic Industries, Ltd., weight average molecular weight=10,000) andResin P2-14 (MEH-7851-SS, a phenol-biphenyldiyl resin, produced by MeiwaPlastic Industries, Ltd., weight average molecular weight=1,600), thealkali solubility was evaluated by the above-described method. Theresults are shown in Table 3 below.

TABLE 3 Resin P2-1 P2-2 P2-3 P2-4 P2-5 P2-6 P2-7 P2-8 P2-9 P2-10 P2-11P2-12 P2-13 P2-14 Alkali dissolution 1.7 2.2 2.6 2.8 3.6 12.3 15.5 2.11.9 3.5 3.2 5.0 0.0 5.9 rate [*10⁻² um/sec] Evaluation of alkali goodgood good good good good good good good good good good bad goodsolubility

Preparation and Evaluation of Positive-Type Photosensitive ResinComposition Example 21

100 Parts by mass of Resin (P2-1) obtained in Synthesis Example 12 and11 parts by mass of Photoacid Generator (B-1) were dissolved in 114parts by mass of γ-butyrolactone (GBL), and the solution was filteredthrough a 0.1 μm filter to prepare a positive-type photosensitive resincomposition. The resin composition was evaluated for the cured reliefpattern profile and tensile elongation. The evaluation results are shownin Table 4.

Example 22

Preparation and evaluation were carried out in the same manner as inExample 1, except that 10 parts by mass of Crosslinking Agent (C-1) wasfurther added in Example 21. The evaluation results are shown in Table4.

Examples 23 to 32

Compositions were prepared and evaluated in the same manner as inExample 22, except that Resin P2-1 was replaced by Resins P2-2 to P2-11as shown in Table 4. The evaluation results are shown in Table 4.

Example 33

100 Parts by mass of Resin (P2-3), 5 parts by mass of PhotoacidGenerator (B-2) and 15 parts by mass of Crosslinking Agent (C-1) weredissolved in 114 parts by mass of GBL, and the solution was filteredthrough a 0.1 μm filter to prepare a negative-type photosensitive resincomposition. The resin composition was evaluated for the cured reliefpattern profile and tensile elongation. The evaluation results are shownin Table 4.

Example 34

Preparation and evaluation were carried out in the same manner as inExample 24, except that the amount added of Photosensitizing Agent B-1was changed to 20 parts by mass in Example 24. The evaluation resultsare shown in Table 4.

Example 35

Preparation and evaluation were carried out in the same manner as inExample 24, except that the amount added of Crosslinking Agent C-1 waschanged to 40 parts by mass in Example 24. The evaluation results areshown in Table 4.

Example 36

Preparation and evaluation were carried out in the same manner as inExample 24, except that 20 parts by mass of Crosslinking Agent C-2 wasadded in place of Crosslinking Agent C-1 in Example 24. The evaluationresults are shown in Table 4.

Example 37

Preparation and evaluation were carried out in the same manner as inExample 24, except that 20 parts by mass of Crosslinking Agent C-3 wasadded in place of Crosslinking Agent C-1 in Example 24. The evaluationresults are shown in Table 4.

Example 38

Preparation and evaluation were carried out in the same manner as inExample 24, except that 15 parts by mass of Crosslinking Agent C-4 wasadded in place of Crosslinking Agent C-1 in Example 24. The evaluationresults are shown in Table 4.

Example 39

Preparation and evaluation were carried out in the same manner as inExample 24, except that 10 parts by mass of Crosslinking Agent C-5 wasadded in place of Crosslinking Agent C-1 in Example 24. The evaluationresults are shown in Table 4.

Example 40

Preparation and evaluation were carried out in the same manner as inExample 24, except that 4 parts by mass of Thermal Acid Generator (D-1)was further added and evaluation was carried out at a curing temperatureof 200° C. in Example 24. The evaluation results are shown in Table 4.

Example 41

Preparation and evaluation were carried out in the same manner as inExample 24, except that evaluation was carried out at a curingtemperature of 200° C. in Example 24. The evaluation results are shownin Table 4.

Example 42

Preparation and evaluation were carried out in the same manner as inExample 26, except that 15 parts by mass of Photoacid Generator B-3 wasadded in place of Photoacid Generator B-1 in Example 26. The evaluationresults are shown in Table 4.

Example 43

Preparation and evaluation were carried out in the same manner as inExample 26, except that 57 parts by mass of GBL and 57 parts by mass oftetrahydrofurfuryl alcohol were added in place of 114 parts by mass ofGBL in Example 26. The evaluation results are shown in Table 4

Example 44

Preparation and evaluation were carried out in the same manner as inExample 26, except that 5 parts by mass of phthalic acid was furtheradded in Example 26. The evaluation results are shown in Table 4.

Example 45

Preparation and evaluation were carried out in the same manner as inExample 26, except that 5 parts by mass of pyromellitic acid was furtheradded in Example 26. The evaluation results are shown in Table 4.

Comparative Example 5

Preparation and evaluation were carried out in the same manner as inExample 21, except that Resin P2-1 was replaced by Resin (P2-12) inExample 21. With respect to the cured relief pattern profile, thepattern was buried, and the evaluation was “bad”. The evaluation resultsare shown in Table 4.

Comparative Example 6

Preparation and evaluation were carried out in the same manner as inExample 21, except that Resin P2-1 was replaced by Resin (P2-13) inExample 21. With respect to the cured relief pattern profile, a reliefpattern could not be formed due to insufficient alkali solubility,failing in evaluation. The evaluation results are shown in Table 4.

Comparative Example 7

Preparation and evaluation were carried out in the same manner as inExample 21, except that Resin P2-1 was replaced by Resin (P2-14) inExample 21. With respect to the cured relief pattern profile, thepattern was buried, and the evaluation was “bad”. The evaluation resultsare shown in Table 4.

Comparative Example 8

Preparation and evaluation were carried out in the same manner as inExample 22, except that Resin P2-1 was replaced by Resin (P2-14) inExample 22. With respect to the cured relief pattern profile, thepattern was buried, and the evaluation was “bad”. The evaluation resultsare shown in Table 4.

TABLE 4 Example 21 22 23 24 25 26 27 28 29 30 Polymer (100 parts bymass) P2-1 P2-1 P2-2 P2-3 P2-4 P2-5 P2-6 P2-7 P2-8 P2-9 PhotoacidGenerator B-1 11 11 11 11 11 11 11 11 11 11 (parts by mass) PhotoacidGenerator B-2 (parts by mass) Photoacid Generator B-3 (parts by mass)Crosslinking Agent C-1 10 10 10 10 10 10 10 10 10 (parts by mass)Crosslinking Agent C-2 (parts by mass) Crosslinking Agent C-3 (parts bymass) Crosslinking Agent C-4 (parts by mass) Crosslinking Agent C-5(parts by mass) Thermal Acid Generator D-1 (parts by mass) GBL 114 114114 114 114 114 114 114 114 114 Tetrahydrofurfuryl alcohol Phthalic acidPyromellitic acid Cured relief pattern good good good good good goodgood good good good profile Elongation [%] 14 69 67 66 52 36 38 36 47 42Curing temperature [° C.] 225 225 225 225 225 225 225 225 225 225Example 31 32 33 34 35 36 37 38 39 40 Polymer (100 parts by mass) P2-10P2-11 P2-3 P2-3 P2-3 P2-3 P2-3 P2-3 P2-3 P2-3 Photoacid Generator B-1 1111 20 11 11 11 11 11 11 (parts by mass) Photoacid Generator B-2 5 (partsby mass) Photoacid Generator B-3 (parts by mass) Crosslinking Agent C-110 10 15 10 40 10 (parts by mass) Crosslinking Agent C-2 20 (parts bymass) Crosslinking Agent C-3 20 (parts by mass) Crosslinking Agent C-415 (parts by mass) Crosslinking Agent C-5 10 (parts by mass) ThermalAcid Generator D-1 4 (parts by mass) GBL 114 114 114 114 114 114 114 114114 114 Tetrahydrofurfuryl alcohol Phthalic acid Pyromellitic acid Curedrelief pattern good good good good good good good good good good profileElongation [%] 32 30 57 52 42 35 28 35 58 42 Curing temperature [° C.]225 225 225 225 225 225 225 225 225 200 Example Comparative Example 4142 43 44 45 5 6 7 8 Polymer (100 parts by mass) P2-3 P2-5 P2-5 P2-5 P2-5P2-12 P2-13 P2-14 P2-14 Photoacid Generator B-1 11 11 11 11 11 11 11 11(parts by mass) Photoacid Generator B-2 (parts by mass) PhotoacidGenerator B-3 15 (parts by mass) Crosslinking Agent C-1 10 10 10 10 1010 (parts by mass) Crosslinking Agent C-2 (parts by mass) CrosslinkingAgent C-3 (parts by mass) Crosslinking Agent C-4 (parts by mass)Crosslinking Agent C-5 (parts by mass) Thermal Acid Generator D-1 (partsby mass) GBL 114 114 57 114 114 114 114 114 114 Tetrahydrofurfurylalcohol 57 Phthalic acid 5 Pyromellitic acid 5 Cured relief pattern goodgood good good good bad — bad bad profile Elongation [%] 24 25 22 24 243 5 3 22 Curing temperature [° C.] 200 225 225 225 225 225 225 225 225

Results shown in Table 4 reveal that in Examples 21 to 45, tensileelongation of the cured film is excellent, pattern formation with athick film is possible, and a resin film ensuring a good cured reliefpattern profile is formed.

Synthesis Example 23 Synthesis of Resin P3-1

A 1.0 L-volume separable flask with a Dean-Stark device was purged withnitrogen and thereafter, in the separable flask, 81.3 g (0.738 mol) ofresorcin, 84.8 g (0.35 mol) of 4,4′-bis(methoxymethyl)biphenyl(hereinafter, referred to as “BMMB”), 3.81 g (0.02 mol) ofp-toluenesulfonic acid, and 150 g of propylene glycol monomethyl ether(PGME) were mixed and stirred at 50° C. to dissolve solids.

The mixed solution dissolved was heated to 120° C. in an oil bath, andgeneration of methanol was confirmed by the reaction solution. Afterstirring the reaction solution for 3 hours while maintaining 120° C.,the solution was cooled to room temperature.

Subsequently, 12.3 g (purity content: 0.15 mol) of a formaldehydesolution (37%) in a separate vessel was added dropwise over 1 hour tothe separable flask by using a dropping funnel. After the dropwiseaddition, the temperature was raised to 60° C., and the system wasfurther stirred for 2 hours.

After the completion of reaction, the reaction vessel was cooled in theatmosphere, and 50 g of PGME was separately added thereto and stirred.The resulting diluted reaction solution was added dropwise to 8 L ofwater with high-speed stirring to disperse and precipitate a resin, andthe resin was recovered, appropriately washed with water, dewatered andthen vacuum-dried to obtain Resin (P3-1) at a yield of 82%. The weightaverage molecular weight by GPC of Resin (P3-1) synthesized was 8,700 interms of polystyrene.

Synthesis Example 24 Synthesis of Resin P3-2

A 1.0 L-volume separable flask with a Dean-Stark device was purged withnitrogen and thereafter, in the separable flask, 91.8 g (0.833 mol) ofresorcin, 109.0 g (0.45 mol) of BMMB, 3.81 g (0.02 mol) ofp-toluenesulfonic acid, and 150 g of propylene glycol monomethyl ether(PGME) were mixed and stirred at 50° C. to dissolve solids.

The mixed solution dissolved was heated to 120° C. in an oil bath, andgeneration of methanol was confirmed by the reaction solution. Afterstirring the reaction solution for 3 hours while maintaining 120° C.,the solution was cooled to room temperature.

Subsequently, 4.1 g (pure content: 0.050 mol) of a formaldehyde solution(37%) in a separate vessel was added dropwise over 1 hour to theseparable flask by using a dropping funnel. After the dropwise addition,the temperature was raised to 60° C., and the system was further stirredfor 2 hours.

After the completion of reaction, the same processing as in SynthesisExample 23 was carried out to obtain Resin (P3-2) at a yield of 74%. Theweight average molecular weight by GPC of Resin (P3-2) synthesized was6,400 in terms of polystyrene.

Synthesis Example 25 Synthesis of Resin P3-3

A 1.0 L-volume separable flask with a Dean-Stark device was purged withnitrogen and thereafter, in the separable flask, 85.6 g (0.778 mol) ofresorcin, 96.9 g (0.40 mol) of BMMB, 3.81 g (0.02 mol) ofp-toluenesulfonic acid, and 150 g of propylene glycol monomethyl ether(PGME) were mixed and stirred at 50° C. to dissolve solids.

The mixed solution dissolved was heated to 120° C. in an oil bath, andgeneration of methanol was confirmed by the reaction solution. Afterstirring the reaction solution for 3 hours while maintaining 120° C.,the solution was cooled to room temperature.

Subsequently, 8.2 g (pure content: 0.10 mol) of a formaldehyde solution(37%) in a separate vessel was added dropwise over 1 hour to theseparable flask by using a dropping funnel. After the dropwise addition,the temperature was raised to 60° C., and the system was further stirredfor 2 hours.

After the completion of reaction, the same processing as in SynthesisExample 23 was carried out to obtain Resin (P3-3) at a yield of 83%. Theweight average molecular weight by GPC of Resin (P3-3) thus synthesizedwas 8,200 in terms of polystyrene.

Synthesis Example 26 Synthesis of Resin P3-4

A 1.0 L-volume separable flask with a Dean-Stark device was purged withnitrogen and thereafter, in the separable flask, 78.0 g (0.708 mol) ofresorcin, 72.7 g (0.30 mol) of BMMB, 3.81 g (0.02 mol) ofp-toluenesulfonic acid, and 150 g of propylene glycol monomethyl ether(PGME) were mixed and stirred at 50° C. to dissolve solids.

The mixed solution dissolved was heated to 120° C. in an oil bath, andgeneration of methanol was confirmed by the reaction solution. Afterstirring the reaction solution for 3 hours while maintaining 120° C.,the solution was cooled to room temperature.

Subsequently, 16.4 g (0.200 mol) of a formaldehyde solution (37%) in aseparate vessel was added dropwise over 1 hour to the separable flask byusing a dropping funnel. After the dropwise addition, the temperaturewas raised to 60° C., and the system was further stirred for 2 hours.

After the completion of reaction, the same processing as in SynthesisExample 23 was carried out to obtain Resin (P3-4) at a yield of 82%. Theweight average molecular weight by GPC of Resin (P3-4) synthesized was10,200 in terms of polystyrene.

Synthesis Example 27 Synthesis of Resin P3-5

A 1.0 L-volume separable flask with a Dean-Stark device was purged withnitrogen and thereafter, in the separable flask, 73.7 g (0.68 mol) ofresorcin, 48.5 g (0.20 mol) of BMMB, 3.81 g (0.02 mol) ofp-toluenesulfonic acid, and 150 g of propylene glycol monomethyl ether(PGME) were mixed and stirred at 50° C. to dissolve solids.

The mixed solution dissolved was heated to 120° C. in an oil bath, andgeneration of methanol was confirmed by the reaction solution. Afterstirring the reaction solution for 3 hours while maintaining 120° C.,the solution was cooled to room temperature.

Subsequently, 24.6 g (pure content: 0.300 mol) of a formaldehydesolution (37%) in a separate vessel was added dropwise over 1 hour tothe separable flask by using a dropping funnel. After the dropwiseaddition, the temperature was raised to 60° C., and the system wasfurther stirred for 2 hours.

After the completion of reaction, the same processing as in SynthesisExample 1 was carried out to obtain Resin (P3-5) at a yield of 74%. Theweight average molecular weight by GPC of Resin (P3-5) synthesized was13,900 in terms of polystyrene.

Synthesis Example 28 Synthesis of Resin P3-6

A 1.0 L-volume separable flask with a Dean-Stark device was purged withnitrogen and thereafter, in the separable flask, 88.3 g (0.700 mol) ofpyrogallol, 96.9 g (0.40 mol) of BMMB, 3.81 g (0.02 mol) ofp-toluenesulfonic acid, and 150 g of propylene glycol monomethyl ether(PGME) were mixed and stirred at 50° C. to dissolve solids.

The mixed solution dissolved was heated to 115° C. in an oil bath, andgeneration of methanol was confirmed by the reaction solution. Afterstirring the reaction solution for 3 hours while maintaining 120° C.,the solution was cooled to room temperature.

Subsequently, 8.2 g (pure content: 0.10 mol) of a formaldehyde solution(37%) in a separate vessel was added dropwise over 1 hour to theseparable flask by using a dropping funnel. After the dropwise addition,the temperature was raised to 60° C., and the system was further stirredfor 2 hours.

After the completion of reaction, the same processing as in SynthesisExample 23 was carried out to obtain Resin (P3-6) at a yield of 80%. Theweight average molecular weight by GPC of Resin (P3-6) synthesized was10,600 in terms of polystyrene.

Synthesis Example 29 Synthesis of Resin P3-7

A 1.0 L-volume separable flask with a Dean-Stark device was purged withnitrogen and thereafter, in the separable flask, 119.7 g (0.738 mol) ofphloroglucinol dihydrate, 109.0 g (0.45 mol) of BMMB, 3.81 g (0.02 mol)of p-toluenesulfonic acid, and 150 g of propylene glycol monomethylether (PGME) were mixed and stirred at 50° C. to dissolve solids.

The mixed solution dissolved was heated to 120° C. in an oil bath, andgeneration of methanol was confirmed by the reaction solution. Afterstirring the reaction solution for 3 hours while maintaining 120° C.,the solution was cooled to room temperature.

Subsequently, 4.1 g (pure content: 0.050 mol) of a formaldehyde solution(37%) in a separate vessel was added dropwise over 1 hour to theseparable flask by using a dropping funnel. After the dropwise addition,the temperature was raised to 60° C., and the system was further stirredfor 2 hours.

After the completion of reaction, the same processing as in SynthesisExample 23 was carried out to obtain Resin (P3-7) at a yield of 71%. Theweight average molecular weight by GPC of Resin (P3-7) synthesized was18,600 in terms of polystyrene.

Synthesis Example 30 Synthesis of Resin P3-8

A 1.0 L-volume separable flask with a Dean-Stark device was purged withnitrogen and thereafter, in the separable flask, 82.6 g (0.750 mol) ofresorcin, 84.8 g (0.350 mol) of BMMB, 3.81 g (0.02 mol) ofp-toluenesulfonic acid, and 150 g of propylene glycol monomethyl ether(PGME) were mixed and stirred at 50° C. to dissolve solids.

The mixed solution dissolved was heated to 120° C. in an oil bath, andgeneration of methanol was confirmed by the reaction solution. Afterstirring the reaction solution for 3 hours while maintaining 120° C.,the solution was cooled to room temperature.

Subsequently, 8.7 g (0.150 mol) of propionaldehyde and 50 g of PGME weremixed and stirred in a separate vessel, and the resulting uniformlydissolved solution was added dropwise over 1 hour to the separable flaskby using a dropping funnel. After the dropwise addition, the temperaturewas raised to 60° C., and the system was further stirred for 2 hours.

After the completion of reaction, the same processing as in SynthesisExample 23 was carried out to obtain Resin (P3-8) at a yield of 82%. Theweight average molecular weight by GPC of Resin (P3-8) synthesized was8,500 in terms of polystyrene.

Synthesis Example 31 Synthesis of Resin P3-9

A 1.0 L-volume separable flask with a Dean-Stark device was purged withnitrogen and thereafter, in the separable flask, 84.0 g (0.763 mol) ofresorcin, 84.8 g (0.350 mol) of BMMB, 3.81 g (0.02 mol) ofp-toluenesulfonic acid, and 150 g of propylene glycol monomethyl ether(PGME) were mixed and stirred at 50° C. to dissolve solids.

The mixed solution dissolved was heated to 120° C. in an oil bath, andgeneration of methanol was confirmed by the reaction solution. Afterstirring the reaction solution for 3 hours while maintaining 120° C.,the solution was cooled to room temperature.

Subsequently, 15.0 g (0.150 mol) of 2-methylvaleraldehyde and 50 g ofPGME were mixed and stirred in a separate vessel, and the resultinguniformly dissolved solution was added dropwise over 1 hour to theseparable flask by using a dropping funnel. After the dropwise addition,the temperature was raised to 60° C., and the system was further stirredfor 2 hours.

After the completion of reaction, the same processing as in SynthesisExample 23 was carried out to obtain Resin (P3-9) at a yield of 81%. Theweight average molecular weight by GPC of Resin (P3-9) synthesized was8,400 in terms of polystyrene.

Synthesis Example 32 Synthesis of Resin P3-10

A 1.0 L-volume separable flask with a Dean-Stark device was purged withnitrogen and thereafter, in the separable flask, 89.5 g (0.813 mol) ofresorcin, 84.8 g (0.350 mol) of BMMB, 3.81 g (0.02 mol) ofp-toluenesulfonic acid, and 150 g of propylene glycol monomethyl ether(PGME) were mixed and stirred at 50° C. to dissolve solids.

The mixed solution dissolved was heated to 120° C. in an oil bath, andgeneration of methanol was confirmed by the reaction solution. Afterstirring the reaction solution for 3 hours while maintaining 120° C.,the solution was cooled to room temperature.

Subsequently, 27.6 g (0.150 mol) of dodecanal was diluted with 50 g ofPGME in a separate vessel and then added dropwise over 1 hour to theseparable flask by using a dropping funnel. After the dropwise addition,the temperature was raised to 60° C., and the system was further stirredfor 2 hours.

After the completion of reaction, the same processing as in SynthesisExample 23 was carried out to obtain Resin (P3-10) at a yield of 79%.The weight average molecular weight by GPC of Resin (P3-10) synthesizedwas 7,900 in terms of polystyrene.

Synthesis Example 33 Synthesis of Resin P3-11

Synthesis was carried out in the same manner as in Synthesis Example 31by using 18.3 g (0.150 mol) of 5-norbornenecarboxyaldehyde in place of15.0 g (0.150 mol) of 2-methylvaleraldehyde of Synthesis Example 31,whereby Resin (P3-11) was obtained at a yield of 80%. The weight averagemolecular weight by GPC of Resin (P3-11) synthesized was 8,800 in termsof polystyrene.

Synthesis Example 34 Synthesis of Resin P3-12

Synthesis was carried out in the same manner as in Synthesis Example 31by using 18.3 g (0.150 mol) of salicylaldehyde in place of 15.0 g (0.150mol) of 2-methylvaleraldehyde of Synthesis Example 31, whereby Resin(P3-12) was obtained at a yield of 76%. The weight average molecularweight by GPC of Resin (P3-12) synthesized was 8,600 in terms ofpolystyrene.

<Evaluation of Alkali Solubility>

Using Resins P3-1 to P3-12 obtained in Synthesis Examples 23 to 34,Resin P3-13 (EP-4080G, a novolak resin, produced by Asahi OrganicChemicals Industry Co., Ltd., weight average molecular weight=10,600),Resin P-14 (MEH-7851-4H, a phenol-biphenyldiyl resin, produced by MeiwaPlastic Industries, Ltd., weight average molecular weight=10,000) andResin P-15 (MEH-7851-SS, a phenol-biphenyldiyl resin, produced by MeiwaPlastic Industries, Ltd., weight average molecular weight=1,600), thealkali solubility was evaluated by the above-described method. Theresults are shown in Table 5 below.

TABLE 5 Polymer P3-1 P3-2 P3-3 P3-4 P3-5 P3-6 P3-7 P3-8 P3-9 P3-10 P3-11P3-12 P3-13 P3-14 P3-15 Alkali dissolution 3.2 1.9 3.1 2.8 4.1 10.4 14.72.9 2.8 2.5 2.8 2.9 5.0 0.0 5.9 rate [*10⁻² um/sec] Evaluation of alkaligood good good good good good good good good good good good good badgood solubility

Preparation and Evaluation of Positive-Type Photosensitive ResinComposition Example 46

100 Parts by mass of Resin (P3-1) obtained in Synthesis Example 23 and11 parts by mass of Photoacid Generator (B-1) were dissolved in 114parts by mass of γ-butyrolactone (GBL), and the solution was filteredthrough a 0.1 μm filter to prepare a positive-type photosensitive resincomposition. The resin composition was evaluated for the residual filmratio during heat curing, cured relief pattern profile and tensileelongation. The evaluation results are shown in Table 6.

Example 47

Preparation and evaluation were carried out in the same manner as inExample 46, except that 10 parts by mass of Crosslinking Agent (C-1) wasfurther added in Example 46. The evaluation results are shown in Table6.

Examples 48 to 58

Preparation and evaluation were carried out in the same manner as inExample 47, except that Resin P3-1 was replaced by Resins P3-2 to P3-12obtained in Synthesis Examples 24 to 34 as shown in Table 6 in Example47. The evaluation results are shown in Table 6.

Example 59

100 Parts by mass of Resin (P3-1), 5 parts by mass of PhotoacidGenerator (B-2) and 15 parts by mass of Crosslinking Agent (C-1) weredissolved in 114 parts by mass of GBL, and the solution was filteredthrough a 0.1 μm filter to prepare a negative-type photosensitive resincomposition. The resin composition was evaluated for the cured reliefpattern profile and tensile elongation. The evaluation results are shownin Table 6.

Example 60

Preparation and evaluation were carried out in the same manner as inExample 47, except that the amount added of Photoacid Generator B-1 waschanged to 20 parts by mass in Example 47. The evaluation results areshown in Table 6.

Example 61

Preparation and evaluation were carried out in the same manner as inExample 47, except that the amount added of Crosslinking Agent C-1 waschanged to 40 parts by mass in Example 47. The evaluation results areshown in Table 6.

Example 62

Preparation and evaluation were carried out in the same manner as inExample 47, except that 20 parts by mass of Crosslinking Agent C-2 wasadded in place of Crosslinking Agent C-1 in Example 47. The evaluationresults are shown in Table 6.

Example 63

Preparation and evaluation were carried out in the same manner as inExample 47, except that 20 parts by mass of Crosslinking Agent C-3 wasadded in place of Crosslinking Agent C-1 in Example 47. The evaluationresults are shown in Table 6.

Example 64

Preparation and evaluation were carried out in the same manner as inExample 47, except that 15 parts by mass of Crosslinking Agent C-4 wasadded in place of Crosslinking Agent C-1 in Example 47. The evaluationresults are shown in Table 6.

Example 65

Preparation and evaluation were carried out in the same manner as inExample 47, except that 10 parts by mass of Crosslinking Agent C-7 wasadded in place of Crosslinking Agent C-1 in Example 47. The evaluationresults are shown in Table 6.

Examples 66 and 67

Example 66 was carried out in the same manner as in Example 47, exceptthat 4 parts by mass of Thermal Acid Generator (D-1) was further addedand the curing temperature was set to 200° C. in Example 47. Example 67was carried out in the same manner as in Example 47, except that thecuring temperature was set to 200° C. in Example 47. The evaluationresults are shown in Table 6.

Comparative Example 9

Preparation and evaluation were carried out in the same manner as inExample 46, except that Resin P3-1 was replaced by Resin (P3-13) inExample 46. With respect to the cured relief pattern profile, thepattern was buried, and the evaluation was “bad”. The evaluation resultsare shown in Table 6.

Comparative Example 10

Preparation and evaluation were carried out in the same manner as inExample 47, except that Resin P3-1 was replaced by Resin (P3-13) inExample 47. With respect to the cured relief pattern profile, thepattern was buried, and the evaluation was “bad”. The evaluation resultsare shown in Table 6.

Comparative Example 11

Preparation and evaluation were carried out in the same manner as inExample 46, except that Resin P3-1 was replaced by Resin (P3-14) inExample 46. With respect to the cured relief pattern profile, a reliefpattern could not be formed due to insufficient alkali solubility,failing in evaluation. The evaluation results are shown in Table 6.

Comparative Example 12

Preparation and evaluation were carried out in the same manner as inExample 46, except that Resin P3-1 was replaced by Resin (P3-15) inExample 46. With respect to the cured relief pattern profile, thepattern was buried, and the evaluation was “bad”. The evaluation resultsare shown in Table 6.

Comparative Example 13

Preparation and evaluation were carried out in the same manner as inExample 47, except that Resin P3-1 was replaced by Resin (P3-15) inExample 47. With respect to the cured relief pattern profile, thepattern was buried, and the evaluation was “bad”. The evaluation resultsare shown in Table 6.

TABLE 6 Example 46 47 48 49 50 51 52 53 54 55 Polymer (100 parts bymass) P3-1 P3-1 P3-2 P3-3 P3-4 P3-5 P3-6 P3-7 P3-8 P3-9 PhotoacidGenerator B-1 11 11 11 11 11 11 11 11 11 11 Photoacid Generator B-2Crosslinking Agent C-1 10 10 10 10 10 10 10 10 10 Crosslinking Agent C-220 Crosslinking Agent C-3 20 Crosslinking Agent C-4 15 CrosslinkingAgent C-7 10 Thermal Acid Generator D-1 4 Residual film ratio during85.1 86.3 85.3 85.8 86.9 85.7 85.4 86.6 86.5 86.8 curing [%] Curedrelief pattern good good good good good good good good good good profileElongation [%] 10 51 37 46 39 25 29 27 46 42 Curing temperature [° C.]225 225 225 225 225 225 225 225 225 225 Example 56 57 58 59 60 61 62 6364 65 Polymer (100 parts by mass) P3-10 P3-11 P3-12 P3-1 P3-1 P3-1 P3-1P3-1 P3-1 P3-1 Photoacid Generator B-1 11 11 11 20 11 11 11 11 11Photoacid Generator B-2 5 Crosslinking Agent C-1 10 10 10 15 10 40Crosslinking Agent C-2 20 Crosslinking Agent C-3 20 Crosslinking AgentC-4 15 Crosslinking Agent C-7 10 Thermal Acid Generator D-1 Residualfilm ratio during 87 86.7 87.2 87.4 84.9 87.3 86.2 85.4 87.3 88.2 curing[%] Cured relief pattern good good good good good good good good goodgood profile Elongation [%] 32 36 35 41 43 36 41 36 42 48 Curingtemperature [° C.] 225 225 225 225 225 225 225 225 225 225 ExampleComparative Example 66 67 9 10 11 12 13 Polymer (100 parts by mass) P3-1P3-1 P3-13 P3-13 P3-14 P3-15 P3-15 Photoacid Generator B-1 11 11 11 1111 11 11 Photoacid Generator B-2 Crosslinking Agent C-1 10 10 10 10Crosslinking Agent C-2 Crosslinking Agent C-3 Crosslinking Agent C-4Crosslinking Agent C-7 Thermal Acid Generator D-1 4 Residual film ratioduring 87.2 87.7 76.4 81.2 — 85.2 86.8 curing [%] Cured relief patterngood good bad bad — bad bad profile Elongation [%] 45 27 3 4 5 3 22Curing temperature [° C.] 200 200 225 225 225 225 225

It is understood from Table 6 that the photosensitive resin compositionof the present invention is excellent in tensile elongation of the curedfilm, enables pattern formation with a thick film, and provides a resinfilm ensuring a good cured relief pattern profile.

Synthesis Example 35 Synthesis of Resin P4-1

A 1.0 L-volume separable flask with a Dean-Stark device was purged withnitrogen and thereafter, in the separable flask, 83.3 g (0.885 mol) ofphenol, 48.5 g (0.20 mol) of BMMB, 3.81 g (0.02 mol) ofp-toluenesulfonic acid, and 116 g of diglyme (DMDG) were mixed andstirred at 50° C. to dissolve solids.

The mixed solution dissolved was heated to 150° C. in an oil bath, andgeneration of methanol was confirmed by the reaction solution. In thisstate, the reaction solution was stirred at 150° C. for 3 hours, andthen the solution was cooled to 120° C.

Subsequently, 50.5 g (0.300 mol) of 2,6-bis(hydroxymethyl)-p-cresol and450 g of propylene glycol monomethyl ether (PGME) were mixed and stirredin a separate vessel, and the resulting uniformly dissolved solution wasadded dropwise over 1 hour to the separable flask by using a droppingfunnel. After the dropwise addition, the system was further stirred for2 hours.

After the completion of reaction, the reaction vessel was cooled in theatmosphere, and the resulting diluted reaction solution was addeddropwise to 8 L of water with high-speed stirring to disperse andprecipitate a resin, and the resin was recovered, appropriately washedwith water, dewatered and then vacuum-dried to obtain Resin (P4-1) at ayield of 64%. The weight average molecular weight by GPC of Resin (P4-1)synthesized was 4,700 in terms of polystyrene.

Synthesis Example 36 Synthesis of Resin P4-2

A 1.0 L-volume separable flask with a Dean-Stark device was purged withnitrogen and thereafter, in the separable flask, 114.1 g (0.75 mol) ofmethyl 2-hydroxybenzoate, 72.7 g (0.30 mol) of BMMB, 3.81 g (0.02 mol)of p-toluenesulfonic acid, and 116 g of diglyme (DMDG) were mixed andstirred at 50° C. to dissolve solids.

The mixed solution dissolved was heated to 150° C. in an oil bath, andgeneration of methanol was confirmed by the reaction solution. In thisstate, the reaction solution was stirred at 150° C. for 3 hours, andthen the solution was cooled to 120° C.

Subsequently, 33.2 g (0.200 mol) of 2,6-bis(hydroxymethyl)-p-cresol and332 g of PGME were mixed and stirred in a separate vessel, and theresulting uniformly dissolved solution was added dropwise over 1 hour tothe separable flask by using a dropping funnel. After the dropwiseaddition, the system was further stirred for 2 hours.

After the completion of reaction, the reaction vessel was cooled in theatmosphere, and the resulting diluted reaction solution was addeddropwise to 8 L of water with high-speed stirring to disperse andprecipitate a resin, and the resin was recovered, appropriately washedwith water, dewatered and then vacuum-dried to obtain Resin (P4-2) at ayield of 74%. The weight average molecular weight by GPC of Resin (P4-2)synthesized was 6,900 in terms of polystyrene.

Synthesis Example 37 Synthesis of Resin P4-3

A 1.0 L-volume separable flask with a Dean-Stark device was purged withnitrogen and thereafter, in the separable flask, 95.8 g (0.870 mol) ofresorcin, 84.8 g (0.500 mol) of BMMB, 3.81 g (0.02 mol) ofp-toluenesulfonic acid, and 150 g of propylene glycol monomethyl ether(PGME) were mixed and stirred at 50° C. to dissolve solids.

The mixed solution dissolved was heated to 120° C. in an oil bath, andgeneration of methanol was confirmed by the reaction solution. Afterstirring the reaction solution for 3 hours while maintaining 120° C.,the solution was cooled to room temperature.

After the completion of reaction, the reaction vessel was cooled in theatmosphere, and 300 g of PGME was separately added thereto and stirred.The resulting diluted reaction solution was added dropwise to 8 L ofwater with high-speed stirring to disperse and precipitate a resin, andthe resin was recovered, appropriately washed with water, dewatered andthen vacuum-dried to obtain Resin (P4-3) at a yield of 66%. The weightaverage molecular weight by GPC of Resin (P4-3) synthesized was 5,800 interms of polystyrene. FIG. 9 shows the NMR spectrum obtained bydissolving P4-3 in a deuterated dimethylsulfoxide solvent and measuringthe solution by Model JNM-GSX 400 manufactured by JEOL Ltd.

Synthesis Example 38 Synthesis of Resin P4-4

A 1.0 L-volume separable flask with a Dean-Stark device was purged withnitrogen and thereafter, in the separable flask, 60.6 g (0.550 mol) ofresorcin, 84.8 g (0.500 mol) of 2,6-bis(hydroxymethyl)-p-cresol, 3.81 g(0.02 mol) of p-toluenesulfonic acid, and 150 g of propylene glycolmonomethyl ether (PGME) were mixed and stirred at 50° C. to dissolvesolids.

The mixed solution dissolved was heated to 120° C. in an oil bath, andgeneration of methanol was confirmed by the reaction solution. Afterstirring the reaction solution for 3 hours while maintaining 120° C.,the solution was cooled to room temperature.

After the completion of reaction, the reaction vessel was cooled in theatmosphere, and 400 g of PGME was separately added thereto and stirred.The resulting diluted reaction solution was added dropwise to 8 L ofwater with high-speed stirring to disperse and precipitate a resin, andthe resin was recovered, appropriately washed with water, dewatered andthen vacuum-dried to obtain Resin (P4-4) at a yield of 71%. The weightaverage molecular weight by GPC of Resin (P4-4) synthesized was 38,600in terms of polystyrene.

Synthesis Example 39 Synthesis of Resin P4-5

A 1.0 L-volume separable flask with a Dean-Stark device was purged withnitrogen and thereafter, in the separable flask, 59.0 g (0.536 mol) ofresorcin, 3.81 g (0.02 mol) of p-toluenesulfonic acid, and 150 g ofpropylene glycol monomethyl ether (PGME) were mixed and stirred at 40°C. to dissolve solids.

Subsequently, 40.6 g (purity content: 0.50 mol) of a formaldehydesolution (37%) was added dropwise over 1 hour to the separable flask byusing a dropping funnel. After the dropwise addition, the temperaturewas raised to 60° C., and the system was further stirred for 2 hours.

After the completion of reaction, the reaction vessel was cooled in theatmosphere, and 400 g of PGME was separately added thereto and stirred.The resulting diluted reaction solution was added dropwise to 8 L ofwater with high-speed stirring to disperse and precipitate a resin, andthe resin was recovered, appropriately washed with water, dewatered andthen vacuum-dried to obtain Resin (P4-5) at a yield of 82%. The weightaverage molecular weight by GPC of Resin (P4-5) synthesized was 27,900in terms of polystyrene.

Synthesis Example 40 Synthesis of Resin P4-6

A 1.0 L-volume separable flask with a Dean-Stark device was purged withnitrogen and thereafter, in the separable flask, 84.1 g (0.667 mol) ofpyrogallol, 121.2 g (0.500 mol) of BMMB, 3.81 g (0.02 mol) ofp-toluenesulfonic acid, and 150 g of diglyme (DMDG) were mixed andstirred at 50° C. to dissolve solids.

The mixed solution dissolved was heated to 120° C. in an oil bath, andgeneration of methanol was confirmed by the reaction solution. Afterstirring the reaction solution for 3 hours while maintaining 120° C.,the solution was cooled to room temperature.

After the completion of reaction, the reaction vessel was cooled in theatmosphere, and 300 g of PGME was separately added thereto and stirred.The resulting diluted reaction solution was added dropwise to 8 L ofwater with high-speed stirring to disperse and precipitate a resin, andthe resin was recovered, appropriately washed with water, dewatered andthen vacuum-dried to obtain Resin (P4-6) at a yield of 79%. The weightaverage molecular weight by GPC of Resin (P4-6) synthesized was 12,800in terms of polystyrene.

Synthesis Example 41 Synthesis of Resin P4-7

A 1.0 L-volume separable flask with a Dean-Stark device was purged withnitrogen and thereafter, in the separable flask, 67.3 g (0.533 mol) ofpyrogallol, 84.1 g (0.500 mol) of 2,6-bis(hydroxymethyl)p-cresol, 3.81 g(0.02 mol) of p-toluenesulfonic acid, and 150 g of propylene glycolmonomethyl ether (PGME) were mixed and stirred at 50° C. to dissolvesolids.

The mixed solution dissolved was heated to 120° C. in an oil bath, andgeneration of methanol was confirmed by the reaction solution. Afterstirring the reaction solution for 3 hours while maintaining 120° C.,the solution was cooled to room temperature.

After the completion of reaction, the reaction vessel was cooled in theatmosphere, and 400 g of PGME was separately added thereto and stirred.The resulting diluted reaction solution was added dropwise to 8 L ofwater with high-speed stirring to disperse and precipitate a resin, andthe resin was recovered, appropriately washed with water, dewatered andthen vacuum-dried to obtain Resin (P4-7) at a yield of 83%. The weightaverage molecular weight by GPC of Resin (P4-7) synthesized was 45,700in terms of polystyrene.

Synthesis Example 42 Synthesis of Resin P4-8

A 1.0 L-volume separable flask with a Dean-Stark device was purged withnitrogen and thereafter, in the separable flask, 114.1 g (0.750 mol) ofmethyl 2-hydroxybenzoate, 121.2 g (0.500 mol) of BMMB, 3.81 g (0.02 mol)of p-toluenesulfonic acid, and 150 g of diglyme (DMDG) were mixed andstirred at 50° C. to dissolve solids.

The mixed solution dissolved was heated to 150° C. in an oil bath, andgeneration of methanol was confirmed by the reaction solution. Afterstirring the reaction solution for 3 hours while maintaining 150° C.,the solution was cooled to room temperature.

After the completion of reaction, the reaction vessel was cooled in theatmosphere, and 300 g of PGME was separately added thereto and stirred.The resulting diluted reaction solution was added dropwise to 8 L ofwater with high-speed stirring to disperse and precipitate a resin, andthe resin was recovered, appropriately washed with water, dewatered andthen vacuum-dried to obtain Resin (P4-8) at a yield of 76%. The weightaverage molecular weight by GPC of Resin (P4-8) synthesized was 6,600 interms of polystyrene.

Synthesis Example 43 Synthesis of Resin P4-9

A 1.0 L-volume separable flask with a Dean-Stark device was purged withnitrogen and thereafter, in the separable flask, 91.3 g (0.600 mol) ofmethyl 2-hydroxybenzoate, 84.1 g (0.500 mol) of2,6-bis(hydroxymethyl)-p-cresol, 3.81 g (0.02 mol) of p-toluenesulfonicacid, and 150 g of diglyme (DMDG) were mixed and stirred at 50° C. todissolve solids.

The mixed solution dissolved was heated to 130° C. in an oil bath, andgeneration of methanol was confirmed by the reaction solution. Afterstirring the reaction solution for 3 hours while maintaining 130° C.,the solution was cooled to room temperature.

After the completion of reaction, the reaction vessel was cooled in theatmosphere, and 300 g of PGME was separately added thereto and stirred.The resulting diluted reaction solution was added dropwise to 8 L ofwater with high-speed stirring to disperse and precipitate a resin, andthe resin was recovered, appropriately washed with water, dewatered andthen vacuum-dried to obtain Resin (P4-9) at a yield of 76%. The weightaverage molecular weight by GPC of Resin (P4-9) synthesized was 12,100in terms of polystyrene.

<Evaluation of Alkali Solubility>

Polymers P-1 to P-12 were prepared using Resins P4-1 to P4-9 obtained inSynthesis Examples 35 to 42, EP-4080G (P4-10), and/or MEH-7851-SS(P4-11) individually or as a resin mixture at the mixing ratio shown inTable 7 and evaluated for the alkali solubility by the above-describedmethod. The results are shown in Table 7 below.

TABLE 7 Polymer P-1 P-2 P-3 P-4 P-5 P-6 P-7 P-8 P-9 P-10 P-11 P-12 P4-1100 P4-2 100 P4-3 100 50 80 60 40 60 P4-4 50 20 40 60 P4-5 40 P4-6 60P4-7 50 P4-8 60 P4-9 40 P4-10 40 P4-11 50 Alkali 1.2 1.6 1.3 3.0 4.9 1.62.3 2.7 4.1 3.9 5.8 1.4 dissolution rate [*10⁻² um/sec] Evaluation goodgood good good good good good good good good good good of alkalisolubility

Preparation and Evaluation of Photosensitive Resin Composition Example68

100 Parts by mass of Resin (P4-1) obtained in Synthesis Example 35, 5parts by mass of Photoacid Generator (B-2) and 15 parts by mass ofCrosslinking Agent (C-1) were dissolved in 114 parts by mass ofγ-butyrolactone (GBL), and the solution was filtered through a 0.1 μmfilter to prepare a negative-type photosensitive resin composition. Theresin composition was evaluated for the residual film ration during heatcuring, cured relief pattern profile and tensile elongation. Theevaluation results are shown in Table 8.

Example 69

100 Parts by mass of Resin (P4-2) obtained in Synthesis Example 36, 11parts by mass of Photoacid Generator (B-1) and 10 parts by mass ofCrosslinking Agent (C-1) were dissolved in 114 parts by mass ofγ-butyrolactone (GBL), and the solution was filtered through a 0.1 μmfilter to prepare a positive-type photosensitive resin composition. Theresin composition was evaluated for the residual film ration during heatcuring, cured relief pattern profile and tensile elongation. Theevaluation results are shown in Table 8.

Example 70

Preparation and evaluation were carried out in the same manner as inExample 68, except that 100 parts by mass of Resin (P4-1) was replacedby 100 parts by mass of Resin (P4-3) in Example 68. The evaluationresults are shown in Table 8.

Examples 71 and 72

Negative-type photosensitive resin compositions were prepared byblending Resins P4-3, P4-4, P4-10 and P4-11, Photoacid Generator (B-2)and Crosslinking Agent (C-1) at the blending ratio shown in Table 8,dissolving these components in 114 parts by mass of GBL, and filteringthe solution through a 0.1 μm filter and evaluated for the cured reliefpattern profile and tensile elongation. The evaluation results are shownin Table 8.

Examples 73 to 79

Positive-type photosensitive resin compositions were prepared byblending Resins P4-3 to P4-11, Photoacid Generator (B-1) andCrosslinking Agent (C-1) at the blending ratio shown in Table 8,dissolving these components in 114 parts by mass of GBL, and filteringthe solution through a 0.1 μm filter and evaluated for the cured reliefpattern profile and tensile elongation. The evaluation results are shownin Table 8.

Comparative Example 14

Preparation and evaluation were carried out in the same manner as inExample 69, except that 100 parts by mass of Resin (P4-2) was replacedby 50 parts by mass of Resin (P4-10) and 50 parts by mass of Resin(P4-11) in Example 69. With respect to the cured relief pattern profile,the pattern was buried, and the evaluation was “bad”. The evaluationresults are shown in Table 8.

TABLE 8 Example Comparative 68 69 70 71 72 73 74 75 76 77 78 79 Example14 P4-1 100 P4-2 100 P4-3 100 50 80 60 40 60 P4-4 50 20 40 60 P4-5 40P4-6 60 P4-7 50 P4-8 60 P4-9 40 P4-10 50 40 50 P4-11 50 50 50 PhotoacidGenerator B-1 11 11 11 11 11 11 11 11 11 Photoacid Generator B-2 5 5 5 5Crosslinking Agent C-1 15 10 15 15 15 10 10 10 10 10 10 10 10 Curedrelief pattern good good good good good good good good good good goodgood bad profile Elongation [%] 11 19 26 15 13 31 24 17 21 25 19 14 13Curing temperature 225 225 225 225 225 225 225 225 225 225 225 225 225

It is understood from Table 8 that the photosensitive resin compositionof the present invention is excellent in tensile elongation of the curedfilm, enables pattern formation with a thick film, exhibits a highresidual film ratio during curing, and gives a resin film ensuring agood cured relief pattern profile.

With respect to the photosensitive resin compositions of Examples 2, 26,44, 45, 51 and 75 and Comparative Examples 1, 3, 4 and 14, the curingtemperature was set to 200° C., and the tensile elongation measurement,glass transition temperature measurement, residual stress measurementand cross-sectional angle measurement were carried out by theabove-described methods. The evaluation results are shown in Table 9.

TABLE 9 Example Comparative Example 2 26 44 45 51 75 1 3 4 14 Elongation25 32 22 22 25 21 2 5 21 11 [%] Glass 221 212 215 217 214 202 170 81 160197 transition temperature [° C.] Residual 17 12 14 15 14 14 10 4 22 18stress [MPa] Cross- 48 55 74 84 51 41 18 could 12 15 sectional not beangle [°] measured Curing 200 200 200 200 200 200 200 200 200 200temperature [° C.]

INDUSTRIAL APPLICABILITY

The photosensitive resin composition of the present invention can besuitably used as a surface protective film of a semiconductor device, adisplay device and a light-emitting device, an interlayer insulatingfilm, an insulating film for rewiring, a protective film for a flip-chipdevice, a protective film of a device having a bump structure, aninterlayer insulating film of a multilayer circuit, a cover coat of aflexible copper clad laminate, a solder resist film, a liquid crystalalignment film, etc.

1. A photosensitive resin composition comprising: (A-2) a resin mixture including a resin containing a structure represented by following formula (7) and a resin containing a structure represented by following formula (8), and (B) a photoacid generator, wherein the weight ratio of said resin containing a structure represented by formula (7): said resin containing a structure represented by formula (8) is from 5:95 to 95:5:

wherein in formulae (7) and (8), each X is independently a monovalent group selected from the group consisting of a hydrogen atom, an alkoxycarbonyl group having a carbon number of 2 to 20, an alkoxycarbonylmethyl group having a carbon number of 2 to 20, an alkoxyalkyl group having a carbon number of 2 to 20, a silyl group substituted with at least one alkyl group having a carbon number of 1 to 10, a tetrahydropyranyl group, and a tetrahydrofuranyl group; each m₁ is independently an integer of 1 to 3, provided that the plurality of m₁ are not 1 at the same time, each m₂ is independently an integer of 0 to 2, and 2≦(m₁+m₂)≦4; each of m₃ and m₄ is independently an integer of 0 to 4; each of n₁ and n₂ is independently an integer of 1 to 500; each R₁ is independently a monovalent group selected from the group consisting of a hydrocarbon group having a carbon number of 1 to 10, an alkoxy group having a carbon number of 1 to 10, a nitro group, a cyano group, and a group represented by following formula (5) or (6); when m₂ is 2, the plurality of R₁ may be the same as or different from each other; each of R₂ to R₅ is independently a hydrogen atom, a monovalent aliphatic group having a carbon number of 1 to 10, or a monovalent aliphatic group having a carbon number of 1 to 10, in which some hydrogen atoms or all hydrogen atoms are substituted with a fluorine atom; each of R₆ and R₇ is independently a halogen atom, a hydroxyl group or a monovalent organic group; when m₃ is an integer of 2 to 4, the plurality of R₆ may be the same as or different from each other; when m₄ is an integer of 2 to 4, the plurality of R₇ may be the same as or different from each other; Y is a divalent organic group represented by following formula (3) or (4); W is a divalent group selected from the group consisting of a single bond, a chain aliphatic group having a carbon number of 1 to 10, a chain aliphatic group having a carbon number of 1 to 10, in which some hydrogen atoms or all hydrogen atoms are substituted with a fluorine atom, an alicyclic group having a carbon number of 3 to 20, an alicyclic group having a carbon number of 3 to 20, in which some hydrogen atoms or all hydrogen atoms are substituted with a fluorine atom, an alkylene oxide group having from 1 to 20 repeating units, and groups represented by following formula (2):

wherein in formula (3), each of R₈ and R₉ is independently a hydrogen atom, a monovalent organic group having a carbon number of 1 to 11, or a group containing a carboxyl group, a sulfonic acid group or a phenolic hydroxyl group;

wherein in formula (4), each of R₁₁ to R₁₄ is independently a hydrogen atom, a monovalent aliphatic group having a carbon number of 1 to 10, or a monovalent aliphatic group having a carbon number of 1 to 10, in which some hydrogen atoms or all hydrogen atoms are substituted with a fluorine atom; m₅ is an integer of 1 to 4; when m₅ is 1, R₁₀ is a hydroxyl group; when n₅ is an integer of 2 to 4, at least one R₁₀ is a hydroxyl group and the remaining R₁₀ are a halogen atom, a hydroxyl group, or a monovalent organic group; and all R₁₀ may be the same or different;

wherein in formula (5), R₁₅ is a monovalent group selected from the group consisting of a hydroxyl group, an aliphatic group having a carbon number of 1 to 12, an alicyclic group having a carbon number of 3 to 12, an aromatic group having a carbon number of 6 to 18, —NH₂, and groups represented by —NH—R₁₉, —N(R₁₉)₂ and —O—R₁₉ wherein R₁₉ is a monovalent group selected from an aliphatic group having a carbon number of 1 to 12, an alicyclic group having a carbon number of 3 to 12, and an aromatic group having a carbon number of 6 to 18;

wherein in formula (6), each of R₁₆ and R₁₇′ is independently a monovalent group selected from the group consisting of a hydrogen atom, an aliphatic group having a carbon number of 1 to 12, an alicyclic group having a carbon number of 3 to 12, and an aromatic group having a carbon number of 6 to 18, and R₁₆ and R₁₇′ may form a ring.
 2. The photosensitive resin composition according to claim 1, wherein in formulae (7) and (8), all X are a hydrogen atom.
 3. The photosensitive resin composition according to claim 1, wherein said resin containing a structure represented by formula (7) contains a structure represented by following formula (9) and said resin containing a structure represented by formula (8) contains a structure represented by following formula (10):

wherein in formulae (9) and (10), each m₂ is independently an integer of 0 to 2, provided that the plurality of m₂ are not 0 at the same time; each R₁ is independently a monovalent group selected from the group consisting of a nitro group, a cyano group, and a group represented by formula (5) or (6); when m₂ is 2, the plurality of R₁ may be the same as or different from each other; and R₂ to R₇, X, Y, W, m₃, m₄, n₁ and n₂ are as defined in formulae (7) and (8) above.
 4. The photosensitive resin composition according to claim 3, wherein in formulae (9) and (10), all X are a hydrogen atom.
 5. The photosensitive resin composition according to claim 1, wherein Y in formula (8) is a resin containing a structure represented by following formula (11) or (12): —CHR₈—  (11) wherein in formula (11), R₈ is a hydrogen atom or a monovalent organic group having a carbon number of 1 to 11;

wherein in formula (12), R₁₇ is a hydrocarbon group having a carbon number of 1 to 10 or an alkoxy group having a carbon number of 1 to 10, m₆ is an integer of 0 to 3, and when m₆ is 2 or 3, the plurality of R₁₇ may be the same or different.
 6. The photosensitive resin composition according to claim 3, wherein Y in formula (10) is a resin containing a structure represented by formula (11) or (12).
 7. The photosensitive resin composition according to claim 1, wherein R₁ in formulae (7) and (8) is at least one member selected from the group consisting of a hydrocarbon group having a carbon number of 1 to 10, an alkoxy group having a carbon number of 1 to 10, and a group represented by formula (5), W in formula (7) is a single bond, and R₁₅ in formula (5) is a monovalent group selected from the group consisting of a hydroxyl group, —NH₂, and groups represented by —NH—R₁₉, —N(R₁₉)₂ and —O—R₁₉ (wherein R₁₉ is a monovalent group selected from an aliphatic group having a carbon number of 1 to 12, an alicyclic group having a carbon number of 3 to 12, and an aromatic group having a carbon number of 6 to
 18. 8. The photosensitive resin composition according to claim 1, wherein said resin mixture (A-2) is a resin mixture including a resin containing a structure represented by following formula (15) and a resin containing a structure represented by following formula (8a) and the weight ratio of said resin containing a structure represented by formula (15): said resin containing a structure represented by formula (8a) is from 35:65 to 80:20:

wherein in formulae (15) and (8a), m₁ is from 1 to 3; each m₂ is independently an integer of 0 to 2; each of m₃ and m₄ is independently an integer of 0 to 4; each of n₁ and n₂ is independently an integer of 1 to 500; each R₁ is independently a monovalent group having a carbon number of 1 to 10 selected from a hydrocarbon group and an alkoxy group; when m₂ is 2, the plurality of R₁ may be the same as or different from each other; each R₂ to R₅ is independently a hydrogen atom, a monovalent aliphatic group having a carbon number of 1 to 10, or a monovalent aliphatic group having a carbon number of 1 to 10, in which some hydrogen atoms or all hydrogen atoms are substituted with a fluorine atom; each of R₆ and R₇ is independently a halogen atom, a hydroxyl group or a monovalent organic group; when m₃ is from 2 to 4, the plurality of R₆ may be the same as or different from each other; when m₄ is an integer of 2 to 4, the plurality of R₇ may be the same as or different from each other; and Y is a methylene group or a structure represented by following formula (16):


9. The photosensitive resin composition according to claim 1, wherein said photoacid generator (B) is a compound having a naphthoquinonediazide structure.
 10. The photosensitive resin composition according to claim 1 further comprising (C) a crosslinking agent.
 11. The photosensitive resin composition according to claim 1 further comprising (D) a thermal acid generator.
 12. A method for producing a cured relief pattern, comprising the following steps: (1) a step of forming, on a substrate, a photosensitive resin layer containing the photosensitive′ resin composition according to any one of claims 1-11, (2) a step of exposing said photosensitive resin layer to light, (3) a step of removing the exposed area or unexposed area with a developer to obtain a relief pattern, and (4) a step of heat-treating said relief pattern.
 13. A cured relief pattern produced by the method according to claim
 12. 14. A semiconductor device comprising a semiconductor element and a cured film provided on the top of said semiconductor element, wherein said cured film is the cured relief pattern according to claim
 13. 15. A display device comprising a display element and a cured film provided on the top of said display element, wherein said cured film is the cured relief pattern according to claim
 13. 